Open Collections

UBC Theses and Dissertations

UBC Theses Logo

UBC Theses and Dissertations

Oligothiophene coordination polymers and cyclic trinuclear complexes Earl, Lyndsey Diane 2014

Your browser doesn't seem to have a PDF viewer, please download the PDF to view this item.

Item Metadata

Download

Media
24-ubc_2014_spring_earl_lyndsey.pdf [ 28.44MB ]
Metadata
JSON: 24-1.0165852.json
JSON-LD: 24-1.0165852-ld.json
RDF/XML (Pretty): 24-1.0165852-rdf.xml
RDF/JSON: 24-1.0165852-rdf.json
Turtle: 24-1.0165852-turtle.txt
N-Triples: 24-1.0165852-rdf-ntriples.txt
Original Record: 24-1.0165852-source.json
Full Text
24-1.0165852-fulltext.txt
Citation
24-1.0165852.ris

Full Text

Oligothiophene CoordinationPolymers and Cyclic TrinuclearComplexesbyLyndsey Diane EarlB.A., Reed College, 2007A THESIS SUBMITTED IN PARTIAL FULFILLMENT OFTHE REQUIREMENTS FOR THE DEGREE OFDOCTOR OF PHILOSOPHYinThe Faculty of Graduate and Postdoctoral Studies(Chemistry)THE UNIVERSITY OF BRITISH COLUMBIA(Vancouver)January 2014? Lyndsey Diane Earl 2014AbstractSpacial control within solid state materials is a method for controlling their properties. Thisthesis demonstrates the structural and functional control of oligothiophenes within coordina-tion polymers and cyclic trinuclear complexes.Solvothermal and room temperature reaction conditions were used to synthesize oligothio-phene metal-organic frameworks (71?85, 92?98). Appendage of phenyl and n-hexyl groupsto the ?-position of oligothiophene linkers induces structural changes in both the local andextended structures of the coordination polymers. Frameworks are sensitive to the linker func-tionality: phenyl groups promote the formation of 1D and 2D coordination polymers (74, 77,80, 85, 92, 98) while aggregation of n-hexyl groups directs the local and extended structure of2D and 3D materials (75, 78, 81, 94). Manganese(II) terthienyl coordination polymers (96 and97) exist as isomers that form under solvothermal and post-solvothermal conditions, respec-tively.The photoluminescent properties of the coordination polymers generally matches thoseof the proligand. A bathochromic shift in oligothiophene-based emission occurs in 83 whilecompounds 75 and 81 undergo hypsochromic shifts. Quenching of oligothiophene emissionin compound 81 occurs via incomplete energy transfer. The magnetic susceptibility of man-ganese(II) compounds reflects the local structure, and a spin-canting transition is present in theacentric compound 96. Collapse of the framework of 94 prohibits a spin-canting transition.Gold(I) thienyl pyrazolate cyclic trinuclear complexes form dimeric or polymeric speciesin the solid state. Metal-perturbed ligand-based phosphorescence with lifetimes on the orderof 5 ms are found in gold(I) monothienyl pyrazolates (126, 127, 130, 131). Bithienyl com-plexes (128, 129, 132, 133) do not exhibit phosphorescence at 77 K. Density functional theoryconfirms the contributions of gold(I) ions to the electronic structure of the S1 and T1 states.Oxidative polymerization of monothienyl (130) and bithienyl (132 and 133) complexes withn-hexyl derivatives generates conductive thin films.iiPrefaceMaterial in Chapter 2 has been previously published as a full paper: Earl, L. D., Patrick, B.O., Wolf, M. O. CrystEngComm, 2012, 14, 5101?5108. I am the primary author and principalinvestigator under the supervision of Professor Michael Wolf. Dr. Brian Patrick determinedthe solid state molecular structures of 71?73, 76, and 78.Material in Chapter 3 has been previously published as a full paper: Earl, L. D., Patrick, B.O., Wolf, M. O. Inorg. Chem., 2013, 52, 10021?10030. I am the primary author and principalinvestigator under the supervision of Professor Michael Wolf. Dr. Brian Patrick determinedthe solid state molecular structures of 94 and 95.Material in Chapter 4 will be published in the future with the authors: Earl, L. D., Wolf,M. O. I am the primary author and principal investigator under the supervision of ProfessorMichael Wolf. Dr. Brian Patrick determined the solid state molecular structure of 126.iiiTable of ContentsAbstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iiPreface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iiiTable of Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ivList of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . viiList of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ixList of Schemes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xivList of Charts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xvList of Symbols and Abbreviations . . . . . . . . . . . . . . . . . . . . . . . . . . . . xviAcknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxiDedication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxii1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11.2 Coordination Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21.2.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21.2.2 Topology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31.2.3 Electronic Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 51.2.4 Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141.3 Cyclic Trinuclear Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . 171.3.1 Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181.3.2 Electronic properties . . . . . . . . . . . . . . . . . . . . . . . . . . . 211.4 Oligo- and Polythiophenes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231.5 Goals and Scope of Thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262 Luminescent Coordination Polymers . . . . . . . . . . . . . . . . . . . . . . . . 282.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 322.2.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32ivTable of Contents2.2.2 Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 332.2.3 X-Ray Crystallography . . . . . . . . . . . . . . . . . . . . . . . . . 402.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402.3.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402.3.2 Solid State Molecular Structures . . . . . . . . . . . . . . . . . . . . 442.3.3 PXRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 552.3.4 Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . 572.3.5 Electronic Absorption and Emission Spectra . . . . . . . . . . . . . . 572.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 623 Non-Luminescent Coordination Polymers . . . . . . . . . . . . . . . . . . . . . 643.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 643.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663.2.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663.2.2 Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 663.2.3 X-Ray Crystallography . . . . . . . . . . . . . . . . . . . . . . . . . 693.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693.3.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 693.3.2 Solid State Molecular Structures . . . . . . . . . . . . . . . . . . . . 703.3.3 PXRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853.3.4 Thermal Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . 853.3.5 Infrared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . 863.3.6 Magnetic Susceptibility . . . . . . . . . . . . . . . . . . . . . . . . . 863.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 944 Gold(I) Cyclic Trinuclear Complexes . . . . . . . . . . . . . . . . . . . . . . . . 954.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 954.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 984.2.1 General . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 984.2.2 Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 994.2.3 X-Ray Crystallography . . . . . . . . . . . . . . . . . . . . . . . . . 1084.2.4 DFT Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084.3 Results and Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084.3.1 Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084.3.2 Solid State Molecular Structures . . . . . . . . . . . . . . . . . . . . 1104.3.3 Electronic Absorption and Emission Spectra . . . . . . . . . . . . . . 1154.3.4 DFT Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1204.3.5 Cyclic Voltammetry and Electropolymerization . . . . . . . . . . . . . 1274.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1325 Summary and Future Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1345.1 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1345.2 Future Work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136vTable of ContentsBibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138AppendicesA X-Ray Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150B PXRD Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173viList of Tables2.1 Summary of preparation and structure types for crystallographically character-ized compounds 71?82 and 85. . . . . . . . . . . . . . . . . . . . . . . . . . . 442.2 Miller indices of compound 84 and values of 2? (theoretical and experimental). 562.3 Thermogravimetric data for selected compounds. . . . . . . . . . . . . . . . . 572.4 Solid state photoluminescence data for linkers and coordination polymers 71?85. 583.1 Summary of preparation and structure types for crystallographically character-ized compounds 92?98. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 703.2 Thermogravimetric data for selected compounds. . . . . . . . . . . . . . . . . 853.3 IR stretching frequencies of manganese(II) compounds. . . . . . . . . . . . . . 864.1 Solution state absorption data for compounds 118?125 and 130?133 in CH2Cl2at 298 K. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154.2 Emission data for proligands 118?125. . . . . . . . . . . . . . . . . . . . . . . 1164.3 Emission data for gold(I) complexes 126?133 . . . . . . . . . . . . . . . . . . 1164.4 Calculated thienyl pyrazole (T-Pz) and thienyl thienyl (T-T) torsion angles oflinkers 118?125. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1224.5 Energies (eV) of frontier orbitals of 126 and 131 in the singlet state. . . . . . . 1224.6 Electrochemical data of compounds 122?125 and 130?133 vs. SCE (saturatedcalomel electrode). Data were collected at a scan rate of 100 mV s?1 in CH2Cl2with 0.1 M [n-Bu4N][PF6] as the supporting electrolyte. . . . . . . . . . . . . . 1284.7 X-ray photoelectron spectroscopy data for material deposited on ITO after suc-cessive voltammetry cycles of 130?133. . . . . . . . . . . . . . . . . . . . . . 131A.1 Selected crystallographic data for 71 ? 73. . . . . . . . . . . . . . . . . . . . . 152A.2 Selected crystallographic data for 74 ? 77. . . . . . . . . . . . . . . . . . . . . 153A.3 Selected crystallographic data for 79 ? 82. . . . . . . . . . . . . . . . . . . . . 154A.4 Selected crystallographic data for 85 and 92?94. . . . . . . . . . . . . . . . . . 155A.5 Selected crystallographic data for 95?98. . . . . . . . . . . . . . . . . . . . . . 156A.6 Selected crystallographic data for 118, 119, 126, and 131. . . . . . . . . . . . . 157A.7 Selected bond lengths (?) and angles (?) of 71. . . . . . . . . . . . . . . . . . 158A.8 Selected bond lengths (?) and angles (?) of 72. . . . . . . . . . . . . . . . . . 159A.9 Selected bond lengths (?) and angles (?) of 73. . . . . . . . . . . . . . . . . . 159A.10 Selected bond lengths (?) and angles (?) of 74. . . . . . . . . . . . . . . . . . 160A.11 Selected bond lengths (?) and angles (?) of 75. . . . . . . . . . . . . . . . . . 160A.12 Selected bond lengths (?) and angles (?) of 76. . . . . . . . . . . . . . . . . . 161viiList of TablesA.13 Selected bond lengths (?) and angles (?) of 77. . . . . . . . . . . . . . . . . . 161A.14 Selected bond lengths (?) and angles (?) of 79. . . . . . . . . . . . . . . . . . 162A.15 Selected bond lengths (?) and angles (?) of 80. . . . . . . . . . . . . . . . . . 162A.16 Selected bond lengths (?) and angles (?) of 81. . . . . . . . . . . . . . . . . . 163A.17 Selected bond lengths (?) and angles (?) of 82. . . . . . . . . . . . . . . . . . 164A.18 Selected bond lengths (?) and angles (?) of 85. . . . . . . . . . . . . . . . . . 164A.19 Selected bond lengths (?) and angles (?) of 92. . . . . . . . . . . . . . . . . . 165A.20 Selected bond lengths (?) and angles (?) of 93. . . . . . . . . . . . . . . . . . 165A.21 Selected bond lengths (?) and angles (?) of 94. . . . . . . . . . . . . . . . . . 166A.21 Selected bond lengths (?) and angles (?) of 94. . . . . . . . . . . . . . . . . . 167A.22 Selected bond lengths (?) and angles (?) of 95. . . . . . . . . . . . . . . . . . 167A.23 Selected bond lengths (?) and angles (?) of 96. . . . . . . . . . . . . . . . . . 168A.24 Selected bond lengths (?) and angles (?) of 97. . . . . . . . . . . . . . . . . . 168A.25 Selected bond lengths (?) and angles (?) of 98. . . . . . . . . . . . . . . . . . 169A.26 Selected bond lengths (?) and angles (?) of 118. . . . . . . . . . . . . . . . . . 170A.27 Selected bond lengths (?) and angles (?) of 119. . . . . . . . . . . . . . . . . . 170A.28 Selected bond lengths (?) and angles (?) of 126. . . . . . . . . . . . . . . . . . 171A.29 Selected bond lengths (?) and angles (?) of 131. . . . . . . . . . . . . . . . . . 172viiiList of Figures1.1 Examples of links and nodes found in coordination polymers. . . . . . . . . . . 41.2 Common multinuclear secondary building units of first-row transition metals.a) 4-Connected square: Cu4(?3-OH)2(CO2)4(H2O)2 45 b) 6-connected Zn4O(CO2)6 46c) Paddlewheel (6-connected): Zn2(CO2)4N2 47 d) Pinwheel (8-connected): Co3-(CO2)6N2.48 C: black. H: white. N: light blue. O: oxygen. Co: blue. Cu: green.Zn: gray. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51.3 Simplified energy diagram showing the influence of the degree of linker con-jugation on ligand and metal-based states. Adapted from Ref.40 . . . . . . . . . 81.4 Solid state structures of a) 16; b) 17. C: black; N: light blue; O: oxygen; Zn:gray. Hydrogen and fluorine atoms have been omitted for clarity. Adaptedfrom Ref.60 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111.5 Extended structures of a) 36; b) 37. C: black; H: white; N: light blue; O: red;Co: dark blue. Adapted from Ref.78 . . . . . . . . . . . . . . . . . . . . . . . 181.6 Qualitative energy level diagram for oligo- and polythiophenes. . . . . . . . . . 251.7 Extended structures of a) 53; b) 54. Hg ? ? ? Hg contacts are shown in red. C:black. S: yellow. Hg: gray. Adapted from Ref.108 . . . . . . . . . . . . . . . . 272.1 Extended structure of the rigid (left) and flexible (right) isomers of [Zn(T2DC)-(4,4'-bpy)0.5]n (76). Adapted from Ref.125 . . . . . . . . . . . . . . . . . . . . 312.2 Solid state molecular structures of a) 71, b) 72, and c) 73. Hydrogens, disorder,and non-coordinating solvent have been omitted for clarity. Thermal ellipsoidsare shown at 50 % probability. . . . . . . . . . . . . . . . . . . . . . . . . . . 482.3 Solid state molecular structures of a) 74 and b) 75. Hydrogens and non-coordinating solvent have been omitted for clarity. Ellipsoids are shown at50 % probability. c) Simplified extended structure of 74 and 75. . . . . . . . . 492.4 a) Solid state molecular structure and b) the extended structure of 77. Hydro-gens and non-coordinating solvent have been omitted for clarity. Ellipsoids areshown at 50 % probability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 512.5 a) Solid state molecular structure of 80. Hydrogens and non-coordinating sol-vent have been omitted for clarity. Ellipsoids are shown at 50 % probability. b)Simplified extended structure of 80; red: bpe, blue: 68, green: metal center. . . 52ixList of Figures2.6 a) Solid state molecular structure of 81. Hydrogens, n-hexyl chains, and non-coordinating solvent have been omitted for clarity. Ellipsoids are shown at50 % probability. b) The ribbon feature of 81. c) The simplified structure of81. Dashed lines in red and green illustrate the ribbon feature, and the solidblue line represents the linking 3HT2DC2? groups. d) The extended structureof 81. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532.7 Solid state molecular structure of 85. Non O?H hydrogens have been omittedfor clarity. Ellipsoids are shown at 50 % probability. . . . . . . . . . . . . . . . 552.8 PXRD pattern of 84. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562.9 Fluorescence excitation (dashed) and emission (solid) spectra of 68 (1.25?10?5M) and bpe in MeOH, ?ex = 330 nm, ?em = 425 nm. . . . . . . . . . . . . . . . 602.10 Fluorescence excitation (dashed) and emission (solid) spectra of 3:2 68 andbpe in the solid state. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602.11 Fluorescence excitation (dashed) and emission (solid) spectra of 81. . . . . . . 612.12 Proposed energy transfer scheme for 81. . . . . . . . . . . . . . . . . . . . . . 623.1 Solid state molecular structure of 92. a) Asymmetric unit of 92. Hydrogenatoms have been omitted for clarity. Thermal ellipsoids are shown at 50 %probability. b) Extended view of 92 on the ac plane. . . . . . . . . . . . . . . . 743.2 Solid state molecular structure of 94. a) Asymmetric unit; hydrogens, non-coordinating solvent, and n-hexyl chains have been omitted for clarity. Ther-mal ellipsoids are shown at 50 % probability. b) Extended structure of 94viewed from the bc plane. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 763.3 Simplified coordination environments for the manganese trinuclear nodes of a)6-connected [Mn3(T2DC)3(DMF)4]n (99); b) 4-connected compound 94. Col-ored rods illustrate bithienyl linkers with rods of the same color going to thesame trinuclear node. Net topology of c) [Mn3(T2DC)3(DMF)4]n and d) 94. . . 773.4 a) Solid state molecular structure of 95. Non-O?H hydrogens and non-coordi-nating solvent have been removed for clarity. Thermal ellipsoids are shown at50 % probability. b) Extended 2D structure of 95. . . . . . . . . . . . . . . . . 803.5 Solid state molecular structure of 96. a) The asymmetric unit of 96. Hydrogenshave been omitted for clarity. Thermal ellipsoids are shown at 50% probability.b) View of the extended structure along the a axis. c) View of the carboxylate-bridged 2D lattice of Mn2+ centers with terthiophene units removed for clarity. . 813.6 Solid state molecular structure of 97. a) Asymmetric unit; non O?H hydrogenshave been omitted for clarity. Thermal ellipsoids are shown at 50% probability.b) The extended framework of 97. c) The simplified coordination environmentof the manganese(II) center in 97. d) Simplified topology of 97. Gray nodes:Mn2+; pink nodes: T3DC2?. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823.7 Solid state molecular structure of 98. a) Asymmetric unit.; hydrogens havebeen omitted for clarity. Thermal ellipsoids are shown at 50 % probability. b)Binuclear metal center. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84xList of Figures3.8 ?M vs. T (?); ?MT vs. T (?) for a) 92; b) 94. The solid lines show the besttheoretical fit. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 873.9 ?M vs. T (?); ?MT vs. T (?) for a) 96; b) 98. The solid lines show the besttheoretical fit. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 883.10 Low temperature magnetic susceptibility data for 96: ?MT vs. T (a) and ?Mvs. T (b) at various fields. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 913.11 Field dependence on the magnetization of 96 at 2 K. . . . . . . . . . . . . . . . 923.12 FC and ZFC magnetization plots for 96: : ?MT vs. T (a) and ?M vs. T (b) at100 Oe. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 934.1 Jablonski diagram illustrating some accessible decay pathways within cyclictrinuclear complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 964.2 Solid state molecular structures of a) 118; b) 119. Non N?H hydrogens, disor-der, and the other independent molecules of 119 have been omitted for clarity.Thermal ellipsoids are shown at 50 % probability. . . . . . . . . . . . . . . . . 1114.3 a) Solid state molecular structure of 126. Hydrogens and disorder have beenomitted for clarity. Thermal ellipsoids are shown at 50 % probability. Viewsof two molecules of 126 along the b) c-axis; c) b-axis. . . . . . . . . . . . . . . 1124.4 Preliminary solid state molecular structure of 128 viewed along the c-axis. . . . 1134.5 a) Solid state molecular structure of 131. Hydrogens and disorder have beenomitted for clarity. Thermal ellipsoids are shown at 50 % probability. b) Dimerunit of 131. c) Packing of 131. d) Au ? ? ? S contact of two molecules of 131.n-Hexyl chains have been omitted for clarity. . . . . . . . . . . . . . . . . . . 1144.6 Variable temperature solid state photoluminescence spectra of compounds 126and 127. a) Emission spectra of 126 at ?ex = 375 nm (solid line) and ?ex =315 nm (dotted line). b) Emission spectra of 127 at 298 K and 77 K. . . . . . . 1184.7 Variable temperature photoluminescence spectra of compound 131 in a) thesolid state; b) solution. ?ex = 315 nm. . . . . . . . . . . . . . . . . . . . . . . 1194.8 Variable temperature solid state photoluminescence spectra of compounds 128and 129. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1204.9 Excitation (dashed lines) and emission (solid lines) spectra of compound 132at 77 K. a) Solid state photoluminescence spectra. b) Frozen solution statephotoluminescence spectra, in toluene. . . . . . . . . . . . . . . . . . . . . . . 1214.10 Molecular orbital contours for 126 in the singlet state. a) Monomer HOMO. b)Monomer LUMO. c) Dimer HOMO. d) Dimer LUMO. . . . . . . . . . . . . . 1234.11 Molecular orbital contours for the singlet state of monomer and dimeric unit of130. a) Monomer HOMO. b) Monomer LUMO. c) Dimer HOMO. d) DimerLUMO. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1244.12 Molecular orbital contours for the singlet state of monomer and dimeric unitof 128 using X-ray geometry. a) Monomer HOMO. b) Monomer LUMO. c)Dimer HOMO. d) Dimer LUMO. . . . . . . . . . . . . . . . . . . . . . . . . . 125xiList of Figures4.13 Molecular orbital contours for the triplet state of monomer and dimeric unitof 126 using X-ray geometry. a) Monomer HOMO. b) Monomer LUMO. c)Dimer HOMO. d) Dimer LUMO. . . . . . . . . . . . . . . . . . . . . . . . . . 1264.14 Cyclic voltammograms of 122 (blue) and 124 (red) on glassy carbon electrode.Starting potentials of 0.21 V and 0.22 V vs. SCE, respectively, were used. Datawere collected starting in the anodic direction at a scan rate of 100 mV s?1 inCH2Cl2 with 0.1 M [n-Bu4N][PF6] as the supporting electrolyte. . . . . . . . . 1284.15 Successive cyclic voltammograms of 130 on ITO. A starting potential of 0.26 Vvs. SCE was used. Data were collected starting in the anodic direction at a scanrate of 100 mV s?1 in CH2Cl2 with 0.1 M [n-Bu4N][PF6] as the supportingelectrolyte. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1304.16 Successive cyclic voltammograms of 131 on ITO. A starting potential of 0.21 Vvs. SCE was used. Data were collected starting in the anodic direction at a scanrate of 100 mV s?1 in CH2Cl2 with 0.1 M [n-Bu4N][PF6] as the supportingelectrolyte. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1314.17 Cyclic voltammogram of 132 on ITO. A starting potential of 0.22 V vs. SCEwas used. Data were collected starting in the anodic direction at a scan rate of50 mV s?1 in CH2Cl2 with 0.1 M [n-Bu4N][PF6] as the supporting electrolyte. . 1324.18 Cyclic voltammogram of 133 on ITO. A starting potential of 0.23 V vs. SCEwas used. Data were collected starting in the anodic direction at a scan rate of100 mV s?1 in CH2Cl2 with 0.1 M [n-Bu4N][PF6] as the supporting electrolyte. 1334.19 Excitation (dashed) and emission (solid) spectra of polymers of 132 and 133. . 133A.1 Solid state molecular structures of a) 76 and b) 79. Hydrogens and disorder in76 have been omitted for clarity. Ellipsoids are shown at 50 % probability. . . . 150A.2 Solid state molecular structure of 82. Hydrogens and non-coordination solventhave been omitted for clarity. Ellipsoids are shown at 50 % probability. . . . . 151A.3 Solid state molecular structure of 93. Hydrogens and non-coordination solventhave been omitted for clarity. Ellipsoids are shown at 50 % probability. . . . . 151B.1 Experimental (red) and predicted (blue) PXRD patterns of 71. . . . . . . . . . 173B.2 Experimental (red) and predicted (blue) PXRD patterns of 72. . . . . . . . . . 174B.3 Experimental (red) and predicted (blue) PXRD patterns of 73. . . . . . . . . . 174B.4 Experimental (red) and predicted (blue) PXRD patterns of 74. . . . . . . . . . 175B.5 Experimental (red) and predicted (blue) PXRD patterns of 75. . . . . . . . . . 175B.6 Experimental (red) and predicted (blue) PXRD patterns of 76. . . . . . . . . . 176B.7 Experimental (red) and predicted (blue) PXRD patterns of 77. . . . . . . . . . 176B.8 Experimental PXRD pattern of 78. . . . . . . . . . . . . . . . . . . . . . . . . 177B.9 Experimental (red) and predicted (blue) PXRD patterns of 79. . . . . . . . . . 177B.10 Experimental (red) and predicted (blue) PXRD patterns of 80. . . . . . . . . . 178B.11 Experimental (red) and predicted (blue) PXRD patterns of 81. . . . . . . . . . 178B.12 Experimental (red) and predicted (blue) PXRD patterns of 82. . . . . . . . . . 179B.13 Experimental PXRD pattern of 83. . . . . . . . . . . . . . . . . . . . . . . . . 179B.14 Experimental (red) and predicted (blue) PXRD patterns of 85. . . . . . . . . . 180xiiList of FiguresB.15 Experimental (red) and predicted (blue) PXRD patterns of 92. . . . . . . . . . 180B.16 Experimental (red) and predicted (blue) PXRD patterns of 93. . . . . . . . . . 181B.17 Experimental (red) and predicted (blue) PXRD patterns of 94. . . . . . . . . . 181B.18 Experimental (red) and predicted (blue) PXRD patterns of 95. . . . . . . . . . 182B.19 Experimental (red) and predicted (blue) PXRD patterns of 96. . . . . . . . . . 182B.20 Experimental (red) and predicted (blue) PXRD patterns of 97. . . . . . . . . . 183B.21 Experimental (red) and predicted (blue) PXRD patterns of 98. . . . . . . . . . 183B.22 Experimental (red) and predicted (blue) PXRD patterns of 128. . . . . . . . . . 184xiiiList of Schemes1.1 Topologically equivalent but geometrically different 3-connected networks. A-dapted from Ref.44 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61.2 Synthesis of 5?9. Adapted from Ref.56 . . . . . . . . . . . . . . . . . . . . . . 81.3 Synthesis and connectivity of Ru2+/Os2+ and Zn2+ centers of [Zn(M(O2C-bpy)2-2,2'-bpy) ? 2 DMF ? 4 H2O]n (10). Adapted from Ref.57 . . . . . . . . . . . . . 91.4 Synthesis of compound 13 (top) and 15 (bottom). Adapted from Ref.58 . . . . . 101.5 Synthesis of 39. Adapted from Ref.83 . . . . . . . . . . . . . . . . . . . . . . 191.6 Synthesis of 40. Adapted from Ref.85 . . . . . . . . . . . . . . . . . . . . . . 191.7 Cell dimensions of the crystal and mesophase of 46. Adapted from Ref.90 . . . 211.8 Gelation of 50. Adapted from Ref.81 . . . . . . . . . . . . . . . . . . . . . . . 231.9 Electropolymerization of thiophene. . . . . . . . . . . . . . . . . . . . . . . . 242.1 Synthesis of bithiophene dicarboxylic acids 62, 67, and 68. . . . . . . . . . . . 412.2 Synthesis of terthiophene dicarboxylic acids 63 and 70. . . . . . . . . . . . . . 422.3 Synthesis of bis(thienyl)benzene dicarboxylic acid 69. . . . . . . . . . . . . . 422.4 Synthesis of compounds 71?76, 79, 82, 83, and 85. . . . . . . . . . . . . . . . 432.5 Synthesis of compounds 77,78, 80, and 81. . . . . . . . . . . . . . . . . . . . 433.1 Synthesis of 91 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 703.2 Synthesis of coordination polymers 92?98. . . . . . . . . . . . . . . . . . . . . 714.1 Synthetic route for proligands 118?121. . . . . . . . . . . . . . . . . . . . . . 1094.2 Synthetic route for proligands 122?125. . . . . . . . . . . . . . . . . . . . . . 1094.3 Oxidative coupling of proligand to form a a quarterthienyl bis-pyrazole species. 129xivList of Charts1.1 Structure of a Pd2+/4,4'-bpy molecular square (1) and a Cd2+/4,4'-bpy 2-dimen-sional sheet (2). Counterions and non-coordinating solvent have been omittedfor clarity. Adapted from Ref.26,27 . . . . . . . . . . . . . . . . . . . . . . . . 21.2 Coordination environment of the zinc centers within [Zn3(ptc)2(H2O)2]n (3).Ref.53 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71.3 Coordination environment within [Mn(Hbidc)]n (4). Ref.54 . . . . . . . . . . . 71.4 ? and ? isomers of linker tbp found in 18 ? 23. Adapted from Ref.63 . . . . . . 121.5 Metal center coordination of compounds 24 and 25. Ref68,69 . . . . . . . . . . 121.6 Structures of 26, 27, and 28. Ref.71 . . . . . . . . . . . . . . . . . . . . . . . . 131.7 Structure of 29. Ref.72 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141.8 Metal coordination of compound 30. Ref.73 . . . . . . . . . . . . . . . . . . . 151.9 Structure of pydz; changes in the Mn2+ coordination environments of 31?33.74 151.10 Cavity structure of 34. Adapted from Ref.76 . . . . . . . . . . . . . . . . . . . 161.11 Structure of dpyatriz and coordination environment of 35. Ref.77 . . . . . . . . 171.12 Structures of 41 and 42. M = Cu, Ag, Au. Ref.87 . . . . . . . . . . . . . . . . 191.13 Structure of 43, 44, and 45. Ref.88,89 . . . . . . . . . . . . . . . . . . . . . . . 201.14 Structure of functionalized [3-R,5-R'-Cu(Pz)]3 (47) complexes. Ref.82 . . . . . 211.15 Structure of complex 48 and coordination polymer 49. Ref.94 . . . . . . . . . . 221.16 Structure of 51 and 52. Ref.105,107 . . . . . . . . . . . . . . . . . . . . . . . . 262.1 Structure of thiophene linker H2TDC (55) and metal-organic framework [M2+-TDC(4,4'-bpy)]n (56). Adapted from Ref.120 . . . . . . . . . . . . . . . . . . . 292.2 Structure of 57?61. Ref.123 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 302.3 Structure of 63 and 64. Ref.127 . . . . . . . . . . . . . . . . . . . . . . . . . . 322.4 Structure of linkers 62?63 and 65?70. . . . . . . . . . . . . . . . . . . . . . . 412.5 Coordination modes for dicarboxylate linkers. . . . . . . . . . . . . . . . . . . 452.6 Simplified coordination environments of compounds 71?78 and 82. . . . . . . 462.7 Simplified coordination environments of compounds 79?81 and 85. . . . . . . 473.1 Metal center coordination sphere of compounds 86 and 87.167,168 . . . . . . . . 653.2 Triaryl and tetraaryl linkers 88?90.172?174 . . . . . . . . . . . . . . . . . . . . . 663.3 Simplified coordination environments of compounds 92?94. . . . . . . . . . . 733.4 Simplified coordination environments of compounds 95?98. . . . . . . . . . . 784.1 Structures of 100?102. Ref.203 . . . . . . . . . . . . . . . . . . . . . . . . . . 974.2 Structures of 103?107. Ref.204?206 . . . . . . . . . . . . . . . . . . . . . . . . 98xvList of Charts4.3 Structure of thienyl pyrazole proligands 118?125. . . . . . . . . . . . . . . . . 1104.4 Structure of gold(I) cyclic trinuclear complexes 126?133. . . . . . . . . . . . . 1105.1 Example of thienyl pyrazole carboxylic acid (134); thienyl pyrazole carboxylicacid cyclic trinuclear complex (135). . . . . . . . . . . . . . . . . . . . . . . . 1375.2 Structure of 136. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137xviList of Symbols and Abbreviations? chemical shift?em emission wavelength (nm)?ex excitation wavelength (nm)?max wavelength at band maximum (nm)? X-ray linear absorption coefficient; micro? angle of X-ray source with respect to the crystal? density? error (X-ray)? diffraction angle, Weiss constant?C degrees Celsius? degree3HT2 3,3'-dihexyl-2,2'-bithiophene3PhT2 3,3'-diphenyl-2,2'-bithiophene? angstroma. u. arbitrary unitsbdc 1,4-benzenedicarboxylatebodipy boron-dipyrromethenebpdc 4,4'-biphenyldicarboxylatebpe trans-1,2-bis(4-pyridyl)ethylenebpy bipyridineBpz bipyrazolatebr broadbtc 1,3,5-benzenetricarboxylatebtix 1,4-bis(triazol-1-ylmethyl)benzeneC Curie constantcm centimetercm?1 wavenumber, kayserCOF covalent-organic frameworkCP coordination polymerCTC cyclic trinuclear complexD dimensionald doubletdbtb 1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl)benzeneDEF N,N-diethylformamideDFT density functional theoryDMA dimethylaminexviiList of Symbols and AbbreviationsDMF N,N-dimethylformamideDMNB 2,3-dimethyl-2,3-dinitrobutaneDMSO dimethylsulfoxideDNT 2,4-dinitrotoluenedpyatriz 2,4,6-tris-(di(pyridin-2-yl)amino)-1,3,5-triazinedsbd 4'-disulfo-2,2'-bipyridine N,N'-dioxideEI electron ionizationEpa anodic peak potentialEpc cathodic peak potentialEPR electron paramagnetic resonanceeV electron voltF structure factorFC field cooledFT Fourier transformg Lande? valueH23HT2DC 3,3'-dihexyl-2,2'-bithiophene-5,5'-dicarboxylic acidH23PhT2DC 3,3'-diphenyl-2,2'-bithiophene-5,5'-dicarboxylic acidH2DTTDC dithieno[3,2-b:2',3'-d]thiophene-2,6-dicarboxylic acidH2Ph2T3DC 3',4'-diphenyl-2,2':5',2''-terthiophene-5,5''-dicarboxylic acidH2T2DC 2,2'-bithiophene-5,5'-dicarboxylic acidH2T3DC 2,2':5',2''-terthiophene-5,5''-dicarboxylic acidH2TDC thiophene-2,5-dicarboxylic acidH2TPhTDC 1,4-di(5-carboxythiophen-2-yl)benzenehbidc 1H-benzimidazole-5,6-dicarboxylateHBpz tetramethyl-4,4'-bipyrazoleHHTP 2,3,6,7,10,11-hexahydroxytriphenyleneHOMO highest occupied molecular orbitalHPz pyrazolehr hourHz hertzIR InfraredISC intersystem crossingJ magnetic couplingK KelvinkB Boltzmann constantkcal kilocalorieLn lanthanideLUMO lowest unoccupied molecular orbitalM molarm medium (IR), multiplet (NMR)m/z mass to charge ratioMALDI-TOF matrix-assisted laser desorption ionization time of flightMeOH methanolxviiiList of Symbols and Abbreviationsmg milligramMHz megahertzmin minutemL milliliterMLCT metal-ligand charge transferMOF metal-organic frameworkmol moleMOP metal-organic polyhedronMP melting pointmpb methyl 3-(2-pyridyl)benzoatemV millivoltMV2+ methyl viologenn normalNA Avogardo?s number[n-Bu4N][PF6] tetrabutylammonium hexafluorophosphateNLO nonlinear opticsNMR nuclear magnetic resonanceO2C-bpy 2,2'-bipyrdine-4,4'-dicarboxylateo orthoOAc acetateocb o-chlorobenzolateOe OerstedP3HT poly(3-hexylthiophene)p paraPa PascalPEPPSI-IPr 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)-palladium(II) dichloridePh phenylppm parts per millionPpz 4-(pyrid-4'-yl)-3,5-dimethylpyrazolateptc pyridine-2,4,6-tricarboxylatePXRD powder X-ray diffractionpydz pyradizinepyz pyrazinePz pyrazolateR residual factor, reliability factor (X-ray)Ref. referencertcp rctt-tetrakis(4-pyridyl)cyclobutanes second, singlet (NMR), sharp (IR)S0 singlet ground stateS1 first singlet excited stateS nuclear spinSBU secondary building unitxixList of Symbols and AbbreviationsSCE saturated calomel electrodeSCSC single crystal to single crystalSCXRD single crystal X-ray diffractionSHG second harmonic generationSOMO singly occupied molecular orbitalSQUID superconducting quantum interference deviceT thiophenet tripletT temperatureT1 first triplet excited stateTC Curie temperatureTCI Tokyo Chemical IndustryTCNQ tetracyanoquinodimethaneTCNQ(MeO)2 2,5-dimethoxy-7,7,8,8-tetracyanoquinodimethaneTCPP tetra(4-carboxyphenyl)porphyrinTD-DFT time dependent density functional theoryTEA triethylamineTGA thermogravimetric analysisTHF tetrahydrofurantht tetrahydrothiopheneTMPD N,N,N',N'-tetramethyl-p-phenylenediamineTN Ne?el temperaturetpb tris(4-pyridylduryl)boraneTTF tetrathiafulvaleneTTFTB tetrathiafulvalenetetrabezonateU Langevin functionUBC University of British ColumbiaUV ultravioletV voltsVis visiblew weak?M molar magnetic susceptibilityXPS X-ray photoelectron spectroscopyZ number of molecules per crystallographic unit cellZFC zero field cooledxxAcknowledgmentsI am appreciative of the direction, independence, and support Dr. Michael Wolf has providedme during my studies.This thesis would have been far less intelligible without the input from Dr. Parisa Mehrkhoda-vandi. Her feedback on this text forced me to take a step back from the details of my work andlook at my research critically from a more general viewpoint.The bulk of this work would not have been possible without the guidance of Dr. Brian Patrickand Anita Lam in the X-ray crystallography lab. I owe a special thanks to Dr. Jim Britten atMcMaster University and Dr. Charles Campana at Bruker for hosting the Canadian ChemicalCrystallography Workshop and further developing my crystallography skills. The fine folksin the microanalysis lab, NMR facility, Shared Instrument Facility, Electronics Shop, SharedComputing, UBC Building Operations, and Brian Ditchburn in glassblowing have been incred-ibly kind individuals who have been instrumental in helping me complete my research.The Wolf group past and present have been delightful co-workers and have aided my scientificdevelopment. I am especially appreciative of Steph Moore for patiently answering most of myquestions during my first year and Ashlee Howarth for both having a constant supply of candyand being my sounding board during the later years. The MacLachlan group also provided afair amount of camaraderie as well as chemicals and equipment. Angela Crane was the sourceof many useful conversations related to the field of coordination polymers.The people who have kept me in good spirits and of sound mind outside the lab are too numer-ous to list, but I would like to salute Aidan B., Amanda R., Helen H., Maria T., Montse R., andRyan C. in particular for being awesome co-workers and friends.My parents, sister, and brother-in-law have been nothing but encouraging, and I am gratefulfor their love and support.Finally, I have to acknowledge ThomDrane for being the most supportive, patient, entertaining,and understanding partner a person could ever request. He has made the past several yearsworthwhile, and I am thankful for his presence as a colleague and friend.xxiTo Earls + Drane.xxiiChapter 1Introduction1.1 OverviewThe role of structure and its relation to electron and energy transfer processes in photo-voltaics, optoelectronic, and conjugated materials has been explored with the intent of un-derstanding and optimizing model systems and functional devices.1?4 In particular, solid statematerials for energy applications are attractive because of the inefficiencies associated withsolution-based systems.5,6 Orientational control has been used to develop light-harvesting sys-tems such as chlorosome mimics,7 form antenna arrays that exhibit internal charge separation,8and study the relation of distance and position in electron donor-acceptor systems.9?13 Un-derstanding the interplay between structure and function in conjugated materials is achievedthrough judicious use of synthetic methodologies such as self-assembly,14 crystal engineer-ing,15 and controlled polymerization.16?18Coordination polymers, including those with non-covalent interactions,19?21 are useful frame-works for studying the electronic properties of optoelectronic materials because crystallineproducts with solid state molecular structures that can be determined are often formed.22 Re-lationships between the known solid state structure and electronic behavior can then be drawn.In addition, subtle modifications to synthetic conditions or reagents can produce an array ofmaterials with tunable structures and properties.23This thesis explores the synthesis and properties of oligothiophene coordination polymersand cyclic trinuclear complexes. Modifying the ?-position of functionalized thiophenes hasa significant impact on the extended structure of first row transition metal coordination poly-mers and gold(I) pyrazolate cyclic trinuclear complexes. The photoluminescent properties ofboth types of materials will be investigated, and the magnetic properties of non-luminescentcoordination polymers will be addressed.11.2. Coordination PolymersN N PdPd NN NN PdPd N N N NN NNNN N N N = H2N NH2 N N CdCd NN NN CdCd N N N NN NNNN N8+8 NO3- n1 2Chart 1.1: Structure of a Pd2+/4,4'-bpy molecular square (1) and a Cd2+/4,4'-bpy 2-dimensionalsheet (2). Counterions and non-coordinating solvent have been omitted for clarity. Adaptedfrom Ref.26,271.2 Coordination Polymers1.2.1 GeneralInorganic coordination polymers including Hofmann clathrates and Prussian Blue havebeen synthesized and characterized during the past few hundred years.24 The functional prop-erties of these materials were generally limited to magnetism and guest analyte capture. Duringthe 1980s and early 1990s, two research groups helped to lay the foundation for modern coor-dination polymers and metal-organic frameworks by expanding the bridging linker from smallinorganic components to more versatile organic compounds. Hoskins and Robson outlined anode and linker approach to synthesizing a series of cubic diamond lattices containing cyano-bridging organic linkers and 4-coordinate metal centers.25 The synthesis and characterizationof palladium(II)/4,4'-bpy (1) (4,4'-bpy = 4,4'-bipyridine) molecular squares capped with ter-minal chelating groups and cadmium(II)/4,4'-bpy (2) 2-dimensional sheets based on molecularsquares in Fujita?s group helped to bridge the gap between classical inorganic coordinationpolymers and the use of organic linkers to bridge inorganic centers (Chart 1.1).26,27 These ma-terials were determined to have useful functionality such as participating in host-guest chem-istry and catalyzing small molecule transformations. Functional three-dimensional and porousmaterials soon followed28 and opened the door to modern crystalline coordination polymers.Only very recently has the terminology surrounding coordination polymers and contempo-21.2. Coordination Polymersrary metal-organic frameworks been formally reevaluated.29 A coordination polymer (CP) isdefined as a coordination compound extending in at least one dimension through coordinationbonds. Coordination networks are a subset of coordination polymers that extend in one dimen-sion but have cross-links between two or more individual components, for example chains30 orspiro-links.31 A metal-organic framework (MOF) is the same as a coordination polymer withthe additional criterion of having an open framework containing potential spacial voids, thoughno measurement of porosity is necessary to call a material a MOF. Given there are no guide-lines for what constitutes a potential spacial void and surface area measurements are porosityare not the focus of the results presented, the terms coordination polymer and coordinationnetwork will be used primarily throughout text.The accessibility of synthesizing crystalline coordination polymers without the presence ofcounter ions was realized with the use of ditopic linkers with charges that balance the valency ofthe metal center.32 In particular, dicarboxylic acids are well-suited for coordinating to divalentfirst-row transition metals. Other types of organic linkers include phosphonates, sulfonates,azolates, imidazolates, and linkers with combinations of these functional groups.33?35Potential applications of crystalline coordination polymers are numerous including gasand small molecule storage and separation,36 heterogenous catalysis,37 crystal engineering,38second-order non-linear optics,39 luminescence,40 ferroelectrics,41 biomedicine,42 and mag-netic behavior.43 This work focuses on the optoelectronic and magnetic properties of coordi-nation polymers with respect a material?s local and extended structure.1.2.2 TopologyBuilding blocks of coordination networks and multi-dimensional coordination polymerscan be simplified to nodes and links. Figure 1.1 provides a visual description of some or-ganic and inorganic components found within coordination polymers. Nodes are junctionsthat are connected to three or more objects within the coordination polymer. They can bemononuclear metal centers, polynuclear clusters, or organic components. Links are entitieswithin a network that connect only two junctions, specifically nodes. In addition, links andnodes may refer to different chemical or crystallographic features of a coordination compound.Mononuclear metal centers can act as links if coordinating, non-bridging solvent occupies allbut two of the coordination sites (Figure 1.1a). Ditopic linkers such as 4,4'-bipyridine (Fig-ure 1.1b) generally act as links within coordination polymers, and metal clusters (Figure 1.1c)coordinated to several organic linkers act as nodes. Figure 1.1d shows that organic linker 1,4-benzenedicarboxylate can act as either a link or a node depending on the metal-carboxylate31.2. Coordination PolymersM H2OOH2 H2OOH2 NNOO OO or orOO OOM M OO OOM MM Mlink linklink node nodeO OO OMM MOOOOOO OOMM nodea) b) c)d)Figure 1.1: Examples of links and nodes found in coordination polymers.coordination mode.A secondary building unit (SBU) is the inorganic portion of a coordination polymer. Com-partmentalizing metal centers, particularly clusters, is useful for clarifying the extended struc-ture of a material; treating metal clusters as a single SBU rather than individual nodes simplifiesthe topological description of the material. Clusters are modeled as SBUs to describe the chem-ical structure of the coordination polymer accurately.44 Figure 1.2 shows common secondarybuilding units found in coordination polymers. These nodes form geometric connectivities suchas squares (Figure 1.2a),45 octahedra (Figure 1.2b),46 paddlewheels or pseudo-octahedra (Fig-ure 1.2c),47 and 8-connected pinwheels (Figure 1.2d).48 The Zn4O(CO2)6 unit (Figure 1.2b) isfound in cubic frameworks such as MOF-5 ([Zn4O(bdc)3]n, bdc = 1,4-benzenedicarboxylate)(26, Chart 1.6).46 Binuclear paddlewheels (Figure 1.2c) also give octahedral centers, but themolecules at the axial positions are different from the linkers in the equatorial positions, andthe axial molecules may be coordinating solvent rather than a linker.With respect to crystallography, topology is the mathematical representation of atomic ormolecular connectivity.44 It should be noted that topology and geometry are not equivalent.Scheme 1.1 shows two networks with equivalent topology (3-connected nets) but differentgeometries: an array of regular hexagons and staggered rectangles. Topological analysis isused to simplify otherwise complicated structures. Programs such as TOPOS49 are employed41.2. Coordination Polymersa) b)c) d)Figure 1.2: Common multinuclear secondary building units of first-row transition metals. a)4-Connected square: Cu4(?3-OH)2(CO2)4(H2O)2 45 b) 6-connected Zn4O(CO2)6 46 c) Paddle-wheel (6-connected): Zn2(CO2)4N2 47 d) Pinwheel (8-connected): Co3(CO2)6N2.48 C: black.H: white. N: light blue. O: oxygen. Co: blue. Cu: green. Zn: gray.to simplified the connectivity and determine the net topology, including Schla?fli notation,50point symbols, and three letter symbol associated with the topology of coordination polymers.The Reticular Chemistry Structure Resource (RCSR) contains a searchable database of 2D and3D periodic nets and assigns three-letter codes to new crystallographic topologies.51 Withinthis work, mathematical topological analysis will be limited to the purpose of categorizingsynthesized materials.1.2.3 Electronic PropertiesLuminescence in coordination polymers has many possible origins including a ligand,metal, or mixed metal-ligand state, and as a result of a charge-transfer process or the pres-51.2. Coordination PolymersScheme 1.1: Topologically equivalent but geometrically different 3-connected networks. A-dapted from Ref.44ence of external stimuli such as surface functionalization, adsorption-based sensitization, scin-tillation, or excimer formation.40 Other optical properties explored in coordination polymersinclude nonlinear optical (NLO) properties and light-driven post-synthetic modifications.Ligand-based luminescence generally originates from radiative decay from the first singletexcited state (S1) or first triplet excited state (T1) to the singlet ground state (S0) to give fluores-cence and phosphorescence, respectively. Non-radiative processes are assumed to be reduceddrastically compared to the uncoordinated linkers due to the increased rigidity within the coor-dination polymer. The proximity and coordination of the organic components to one another inthe solid state opens the door to charge transfer processes, changes in ?max, and a broadening ofemission features.52 Linker-based emission requires having a metal center that does not quenchluminescence processes, and studies of ligand-based luminescence are usually restricted to d10metal-based coordination polymers including zinc(II), cadmium(II), and copper(I) systems.A report of a 3D coordination polymer [Zn3(ptc)2(H2O)2]n (3, Chart 1.2) (ptc = pyridine-2,4,6-tricarboxylate) notes a 2700 cm?1 bathochromic shift in fluorescence emission in addi-tion to an unquantified enhancement of emission intensity compared to the proligand pyridine-2,4,6-tricarboxylic acid.53 The authors speculate increased ligand rigidity and the solid statearrangement of coordinated ptc can account for the observed red shift, though no further evi-dence is provided.An unusual instance of charge transfer was observed in the manganese(II) coordinationpolymer [Mn(hbidc)]n (4, Chart 1.3) (hbidc = 1H-benzimidazole-5,6-dicarboxylate).54 Emis-sion of proligand 1H-benzimidazole-5,6-dicarboxylic acid occurs at ?max = 440 nm and hasa lifetime of 1.2 ns. Compound 4 shows a broad emission centered at 725 nm and with a61.2. Coordination PolymersNZn1 O1 O2O3O4O5 O6 Zn2Zn2N O1O6 O2O5Zn2 Zn2O4O3 HO7H Zn2O6 O7O4O33Chart 1.2: Coordination environment of the zinc centers within [Zn3(ptc)2(H2O)2]n (3). Ref.53N1N2 O3O1O4O2H MnO1 N1O3 O1 O4=4Chart 1.3: Coordination environment within [Mn(Hbidc)]n (4). Ref.54lifetime of 300 ?s assigned to a metal to ligand charge transfer (MLCT) state. The drasticchange in photoluminescence is attributed to spin-orbit coupling of the manganese(II) centerand enhanced intersystem crossing (ISC) of excited states. Ligand-based phosphorescence ispresumed to not be the source of emission since the luminescence is not sensitive to the pres-ence of oxygen.Lanthanide (III) based emission comes from 4f-4f transitions that are weakly sensitive tothe coordination environment surrounding the lanthanide ion.40 These transitions are forbid-den, and direct excitation of the metal results in weak emission. Strongly absorbing organiclinkers within a coordination polymer can sensitize emission via energy transfer processesknown as the antenna effect or luminescence sensitization.55 As illustrated in Figure 1.3, di-rect excitation into the ligand S1 state can result in linker-based fluorescence to the S0 stateor conversion by intersystem crossing to the T1 state. If the ligand triplet state lies above the71.2. Coordination PolymersEnergyLigandn or ? S0S1?? ISCT1MetalEmissionIncreasedconjugationLigandEmissionMetalFigure 1.3: Simplified energy diagram showing the influence of the degree of linker conjuga-tion on ligand and metal-based states. Adapted from Ref.40NNSSOOO OOO OO 2-3 Ln3+H2O NNSSOOO OOO OO N N SS OOOO OO OOO OOOO OO OS SNNLn OH2OH23-H2OBa2+[Ba2(H2O)4[Ln(dsbd)3(H2O)2](H2O)xCl]nLn = Sm, 5; Eu, 6; Gd, 7; Tb, 8; Dy, 9dsbdScheme 1.2: Synthesis of 5?9. Adapted from Ref.56lanthanide ion excited state, non-radiative energy transfer from the ligand triplet state to themetal ion will result in radiative phosphorescence or non-radiative processes.A stepwise assembly approach was used to synthesize an isostructural series of emissionlanthanide coordination polymers bearing the formula [Ba2(H2O)4[Ln(dsbd)3(H2O)2](H2O)xCl]n(dsbd = 4'-disulfo-2,2'-bipyridine N,N'-dioxide, Ln = Sm3+ (5), Eu3+ (6), Gd3+ (7), Tb3+ (8),Dy3+ (9)).56 Treatment of dsbd with Ln3+ formed an 8-coordinate N,N'-dioxide-bound lan-thanide species. Reacting this with Ba2+ produced the heteronuclear coordination polymer81.2. Coordination PolymersNN MN NN N CO2HCO2HHO2CHO2CZn(NO3)2M = Ru, Os2+ =DMF/H2O90 ?C Zn ZnZn ZnZn Zn10Scheme 1.3: Synthesis and connectivity of Ru2+/Os2+ and Zn2+ centers of [Zn(M(O2C-bpy)2-2,2'-bpy) ? 2 DMF ? 4 H2O]n (10). Adapted from Ref.57with sulfonates bound to Ba2+ (see Scheme 1.2). Strong lanthanide-based emission was ob-served in all compounds except for compound 7 where triplet ligand phosphorescence wasobserved. The energy of the ligand T1 state was found to lie lower in energy than any of Gd3+ionic resonance levels.Evidence for energy transfer occurring within a coordination polymer was demonstratedwithin a mixed Zn2+/Ru2+ framework [Zn(Ru(O2C-bpy)22,2'-bpy) ? 2 DMF ? 4 H2O]n (10,Scheme 1.3) utilizing the classic 2,2'-bipyrdine-4,4'-dicarboxylate (O2C-bpy) as a linker.57Ru2+ sites of compound 10 were doped with Os2+, and time-resolved emission spectroscopywas used to probe the MLCT excited states and energy transfer of Ru2+ to Os2+. Increasingthe percentage of Os2+ shortened the delay of Os-based emission because of the decreaseddistance from Ru2+ to Os2+ sites. Using the crystallographic data to determine the nearest-neighbor Ru?Ru distance, the authors determined that energy transfer occurred 15 times for3D migration and 55 times for 2D migration with average excited state lifetimes of 25 ns and7 ns, respectively.Energy transfer between organic linkers within a coordination polymer has been docu-mented by Hupp and co-workers.58 Two zinc(II) mixed linker coordination polymers were syn-91.2. Coordination PolymersBrBr COOHCOOHHOOCHOOCN HNNNHCOOH COOHCOOHHOOC N B NN NFFZn(NO3)2 ? 6 H2ODMF, 80 ?C Zn(NO3)2 ? 6 H2ODMF, HNO3/EtOH, 80 ?CHNO3/EtOH, 80 ?CN B NN NFF121211141315Scheme 1.4: Synthesis of compound 13 (top) and 15 (bottom). Adapted from Ref.58thesized using tetra(4-carboxyphenyl)porphyrin (TCPP, 11) and dipyridyl bodipy (bodipy, 12)to give [Zn2(Zn-TCPP)(bodipy)]n (13) or non-chromophoric 1,4-dibromo-2,3,5,6-tetrakis(4-carboxyphenyl)benzene (dbtb, 14) and 12 to give [Zn2(dbtb)(bodipy)]n (15) (Scheme 1.4).Compounds 13 and 15 are isostructural 3D networks comprised of Zn(II) paddlewheel SBUswith pyridyl groups at the axial positions and carboxylates at the basal positions. Upon exci-tation into the bodipy absorption band at 520 nm, only photoluminescence assigned to TCPPemission at ?max = 667 nm was observed. There is good overlap of emission and absorptionbands of 11 and 12, respectively, leading to the conclusion that emission is based on resonanceenergy transfer.59 Photoexcitation of 15 results in bodipy-based emission at ?max = 596 nm.Light can be used not only to probe the electronic structure of coordination polymers, butalso to perform post-synthetic modifications of solid state materials. Within coordination poly-mers, post-synthetic photoreactions such as [2 + 2] photocycloaddition make use of moleculescontaining unsaturated groups such as fumarate61 or bpe (trans-1,2-bis(4-pyridyl)ethylene) as alinker. Photocyclization reactions require parallel linkers to be within close proximity and havethe appropriate geometry for cyclization to occur.62 Compound [((F3CCO2)(?-O2CCH3)Zn)2-(bpe)2]n (16, Figure 1.4a) undergoes a single-crystal to single-crystal (SCSC) transformationupon irradiation of bpe to form a coordination polymer, [((F3CCO2)(O2CCH3)Zn)2(rtpc)]n (17,Figure 1.4b), with a rctt-tetrakis(4-pyridyl)cyclobutane (rtpc) linker in place of two bpe link-101.2. Coordination Polymersa) b)Figure 1.4: Solid state structures of a) 16; b) 17. C: black; N: light blue; O: oxygen; Zn: gray.Hydrogen and fluorine atoms have been omitted for clarity. Adapted from Ref.60ers.60 The ability for a complete SCSC transformation from 16 to 17 to occur is attributed to theslip-stacked adjacent ladders and the individual ladder strains being well-separated (7.10 ?).An increase in Zn?Zn distance from 3.747 ? to 4.162 ? is observed upon photocyclization.The field of nonlinear optics has benefitted from crystal engineering of metal-organic frame-works. Crystals belonging to noncentrosymmetric space groups are required for achievingsecond harmonic generation (SHG). A series of cadmium-organoboron coordination polymerswere synthesized using a racemic mixture of a helically chiral tris(4-pyridylduryl)borane (tpb)linker (Chart 1.4) to form [Cd(tpb)X2 ? 2 H2O]n where X = Cl? (18), Br? (19), I? (20), NO?3(21), OAc? (22), or ClO?4 (23).63 A molar ratio of 3:1 ?-tbp/?-tpb is found in all solid statemolecular structures, and the Cd2+ metal centers are chiral. The influence of anion on SHG re-sponse of powder samples was reported, with 20 showing the highest response of 35 times thatof ?-quartz64 and 21 having the lowest response of 11 times ?-quartz. The authors hypothesizethe difference in anion-responsive properties is due to how the anions fluctuate charge transferbetween metal centers and linkers to form the necessary electronic asymmetry.Organic linkers that lack inversion symmetry has been a successful method for synthesizingcoordination polymers with NLO properties. In particular, asymmetric p-pyridylcarboxylatescoordinated to Zn2+ and Cd2+ have a tendency to form noncentrosymmetric diamonoid net-works.65?67 The length of the pyridinecarboxylates controls the degree of interpenetration whichin turn influences second harmonic generation.Photoluminescent sensors rely on external stimuli such as the presence of an analyte ora change in pressure or temperature to cause a change in emission behavior. A 3D coordi-nation polymer composed of cyclometalated Ir(mpb)3 (mpb = methyl 3-(2-pyridyl)benzoate)units connected by Zn4O(CO2)6 SBUs ([(Zn4O(Ir(mpb)2)3) ? 6 DMF ? H2O]n (24, Chart 1.5))111.2. Coordination Polymers B NNN ! - tbpB NNN " - tbpChart 1.4: ? and ? isomers of linker tbp found in 18 ? 23. Adapted from Ref.63N CO2Ir 3 3-= or= Zn4O7+24Ir(mpb)33- ZnNO2 O3O1ZnN O2O1O3 O3O4 ZnNZn 25CO2O2C 2- = bpdcChart 1.5: Metal center coordination of compounds 24 and 25. Ref68,69undergoes fluorescence quenching in the presence of molecular oxygen.68 The material main-tains fair reversibility due to its permanent porosity: a loss of 5 % luminescence intensityafter eight oxygenation/deoxygenation cycles. In thin film samples of [Zn2(bpdc)2(bpe)]n (25)(bpdc = 4,4'-biphenyldicarboxylate), fluorescence quenching of 85 % maximum intensity oc-curs in the span of 10 seconds upon exposure to 2,4-dinitrotoluene (DNT) or 2,3-dimethyl-2,3-121.2. Coordination PolymersOO OO =OZnZn ZnZn = Zn4O7+bdc 26, MOF-5 N+N+ 27, MV2+ NN 28, TMPDChart 1.6: Structures of 26, 27, and 28. Ref.71dinitrobutane (DMNB), both which are associated with explosive materials.69 A red-shift inthe ?max of 25 was observed upon exposure to gaseous analytes, but this phenomenon occurredregardless of the identity of the analyte. The optical bandgap of 25 was determined to be 3.1eV which is sufficient to promote electron transfer from the CP to electron deficient DNT andDMNB. As with 24, compound 25 demonstrates robust porosity and a high surface area thatare necessary for reversible coordination polymer sensors.The ability of coordination polymers to participate in electron transfer processes is of in-terest with applications to electron/hole transport systems, semiconductors, and other energymaterials.70 Electron transfer requires at least one donor and acceptor; both components canoriginate from a metal-organic framework, or a guest donor or acceptor can be incorporated.Photoexcitation of MOF-5 (26) causes the material to adopt a charge-separated state witha lifetime in the microsecond regime.71 Compound 26 is able to reduce methyl viologen (27,MV2+) to the vibrant blue methyl viologen radical cation MV?+ (Chart 1.6). In addition, anelectron transfer process was found to occur between MOF-5 and N,N,N',N'-tetramethyl-p-phenylenediamine (28, TMPD) to generate a phenylenediamine radical. A suspension of MOF-5 was compared to an aqueous solution of Zn2+ and 1,4-benzenedicarboxylate, and electronswere found to photoeject from the excited organic ligand. The bandgap of MOF-5 was calcu-lated to be 3.4 eV, and the overall semiconductor behavior of MOF-5 was found to be similarto TiO2.High charge mobility was found within a zinc(II) coordination polymer with tetrathiafulva-lene tetrabenzoate linkers (29, Chart 1.7).72 Helical stacks of tetrathiafulvalene tetrabenzoateare separated by 3.803(2) ?. Using flash photolysis-time-resolved microwave conductivity andtime-of-flight transient current integration experiments, the charge mobility of the coordination131.2. Coordination PolymersSS SSO2C CO2CO2O2C 4-29Chart 1.7: Structure of 29. Ref.72polymer was determined to be 0.2 cm2 V?1 s?1. The conductivity of the coordination polymeris enhanced by two orders of magnitude compared to tetrathiafulvalene tetrabenzoic acid andcomparable to some polythiophenes used in organic photovoltaics.1.2.4 MagnetismAdsorption and desorption of solvent or analytes can induce seemingly minor changes inthe crystallographic environment of coordination polymers that cause perturbations in mag-netic exchange pathways. Dehydration is a well-established technique for modifying magneticmaterials, but this approach is often irreversible because of the permanent nature of the struc-tural change induced upon dehydration. Coordination polymers containing organic linkers havebeen designed to be both robust and flexible to the insertion and removal of analytes, openingthe door to new magnetic materials.[(Ru2(ocb)4)2TCNQ(MeO)2 ? CH2Cl2]n (30) (ocb = ortho-chlorobenzoate, TCNQ(MeO)2= 2,5-dimethoxy-7,7,8,8-tetracyanoquinodimethane) is a charge transfer compound with anantiferromagnetic ground state at TN < 75 K (TN = Ne?el temperature).73 Upon desolvationof CH2Cl2, compound 30 undergoes a ferromagnetic transition at TC = 56 K (TC = Curietemperature), and the partially desolvated compound exhibits both antiferromagnetic and fer-romagnetic domains. Single-crystal diffraction data was obtained for the desolvated sample:while the unit cell remains nearly identical, the pendant ocb ligand was found to be much moredisordered for dried compound 30. This disorder could disrupt antiferromagnetic alignment ofthe material.Dehydration of [[Mn(pydz)(H2O)2][Mn(H2O)2][Nb(CN)8] ? 2 H2O]n (31, pydz= pyradizine)causes changes manganese(II) coordination environments (Chart 1.9) and magnetic orderingof the material.74 Compound 31 contains hydrogen bonds between one CN and coordinat-ing H2O as well as a non-coordinating nitrogen atom of pydz and coordinating H2O. The141.2. Coordination PolymersOMeMeO NN NNRu Ru 2(ocb) 4(ocb) 4Ru 2 Ru 2(ocb) 4Ru OO OO OOOO O ON N NN = OO ClCl3 0Chart 1.8: Metal coordination of compound 30. Ref.73Mn(1)O pydzH2ONC NCNCH HOH2 Mn(2)OH2CNpydz NCNC Mn(2) NCNC31 32 33Mn(1) OH2CN NCCNNCMn(2)OH2OH2 NCCN NCCN Mn(1)NC NCCNCNpydz CNCNN NpydzChart 1.9: Structure of pydz; changes in the Mn2+ coordination environments of 31?33.74first step in dehydration removes four water molecules per formula unit to give [[Mn(pydz)-(H2O)][Mn(H2O)][Nb(CN)8]]n (32). Partial dehydration causes a CN and non-coordinatingnitrogen atom of pydz to coordinate to manganese centers while the original Mn-pydz bondbreaks. Complete dehydration gives [[Mn2(pydz)][Nb(CN)8]]n (33) and causes changes in theMn(1) coordination sphere and the formation of a Mn-CN interaction. The magnetic orderingtemperature increases with increasing dehydration (31: 43 ?C; 32: 68 ?C; 33: 100 ?C), and themagnetic and structural transformations were found to be completely reversible.Spin crossover systems are those where a physical (light, temperature, pressure) or chemi-cal (adsorption/desorption, oxidation) stimulus induces a transformation from high spin to lowspin or vice versa.75 [Fe(pyz)[Pt(CN)4] ? 2 H2O]n (34, Chart 1.10) (pyz = pyrazine) under-151.2. Coordination PolymersFeN N C Pt C N FeN C PtCN NNNFe FeNCPtCNN C PtC N34Chart 1.10: Cavity structure of 34. Adapted from Ref.76goes hysteretic spin crossover transitions at 285 K (low spin) and 309 K (high spin).76 Guestmolecules were found to reversibly adsorb and desorb into the pores of 34 and could haveno effect (CO2, N2, O2), stabilized the high spin state (5 and 6 membered cyclic molecules,H2O, alcohols), or stabilized the low spin state (CS2). The authors deduced that the shape andsize of the guest molecule as well as how the guest interacts with platinum and pyz within thenear void spaces of the framework dictate if and how the guest stabilizes the spin crossovertransition.[[Fe3(dpyatriz)2(CH3CH2CN)4(BF4)2](BF4)4 ? 4 CH3CH2CN]n (35, Chart 1.11) (dpyatriz= 2,4,6-tris-(di(pyridin-2-yl)amino)-1,3,5-triazine) is a coordination network with 1D chan-nels which facilitate the exchange of coordinating propionitrile molecules.77 Soaking crystalsof 35 in acetonitrile or propanol led to an exchange of molecules in the iron coordinationsphere. In acetonitrile, the transition temperature decreased from 300 K to 273 K; treatmentwith propanol completely suppressed spin crossover, possibly due to a reduced ligand fieldaround Fe2+. Powder X-ray diffraction (PXRD) analysis showered the material maintained itscrystallinity and unit cell dimensions after exposure to acetonitrile and propanol.Physical stimuli have been used to induce structural transformations in coordination poly-mers while maintaining the material?s magnetic properties. Heating of the 1D cationic co-ordination network [(Co(syn-btix)2(H2O)2) ? 2 NO3 ? 2 H2O]n (36, Figure 1.5a) (btix = 1,4-bis(triazol-1-ylmethyl)benzene) displaces both coordinating and non-coordinating H2O andcauses a syn-anti conformation change in btix to generate the neutral 2D coordination poly-mer [Co(anti-btix)2(NO3)2]n (37, Figure 1.5b).78 During this process, metal-nitrogen bondsmust be broken and reformed. Magnetic susceptibility measurements showed that ?MT is in-sensitive to the conformation of btix, and EPR (electron paramagnetic resonance) spectroscopyshowed no intermediate Co2+ coordination spheres formed between the conversion of 36 to 38.161.3. Cyclic Trinuclear Complexes= N N NN NNNN N NNNFe FeFeN N Fe FeFeN N FeFe FeFeN NBF 4BF 4 BF 4BF 435dpyatrizChart 1.11: Structure of dpyatriz and coordination environment of 35. Ref.771.3 Cyclic Trinuclear ComplexesCyclic trinuclear complexes (CTCs) are planar nine-membered rings containing three bridg-ing linkers and three metal (usually d10) centers (Scheme 1.5 and Scheme 1.6). C?N or N?Nlinkers, often but not always cyclic themselves, bridge the metals to create molecules that aretrinuclear; tetranuclear, hexanuclear, or polymeric species are formed depending on syntheticconditions and ligand design.79 The structural80 (solid state packing, liquid crystal behav-ior, crystal engineering) and electronic81,82 (thermoluminescence, metallophilic interactions,?-donor/acceptor character) properties associated with cyclic trinuclear complexes containingcoinage metals (Cu+, Ag+, Au+) have resulted in a rich and ever expanding area of research forthis class of materials.The first example of a gold(I) CTC, reported in 1970, was obtained from the reaction oftriphenylarsine gold(I) chloride with 2-pyridyl lithium (39, Scheme 1.5).83 Imidazolates can171.3. Cyclic Trinuclear Complexesa)b)Figure 1.5: Extended structures of a) 36; b) 37. C: black; H: white; N: light blue; O: red; Co:dark blue. Adapted from Ref.78also be used to generate C?N gold (I) tricycles using a lithiated alkyl 2-imidazole in the pres-ence of either Ph3AsAuCl or (CH3)2SAuCl.84 Deprotonation of pyrazoles with a base such asNaH or triethylamine (TEA) in the presence of a gold(I) reagent, often AuCl(tht), will givecyclic trinuclear species [Au(Pz)]3 (40, Scheme 1.6).851.3.1 StructureThe local and extended structure of cyclic trinuclear complexes are dictated by the sub-stituents on the bridging ligand. A series of CTCs with isopropyl and tert-butyl groups atthe 3 and 5 positions of the bridging pyrazolate was synthesized.86 Fujisawa and co-workersfound coinage metal complexes with 3,5-diisopropylpyrazolate formed trinuclear molecules,those with 3-tert-butyl-5-isopropylpyrazolate formed a mix of trinuclear (Ag+) and tetranuclear(Cu+, Au+) species, while use of 3,5-di-tert-butylpyrazolates gave tetranuclear compounds for181.3. Cyclic Trinuclear Complexes N AuAu NAuNN Li +      3    Ph3AsAuCl3 THF, -40 ?C 39Scheme 1.5: Synthesis of 39. Adapted from Ref.83NNH +      3    AuCl(tht)3 N NAuAuN NN Au NTHF, N(Et)3 4 0Scheme 1.6: Synthesis of 40. Adapted from Ref.85all coinage metals. Cyclic hexanuclear complexes (41, M = Cu, Ag, Au) can be synthesizedfrom enantiomerically pure 2,2'-di(1,2-pyrazol-3-yl)-1,1'-binaphthalene (42) which has twopyrazole moieties per molecule (Chart 1.12). Molecules of 41 crystallize with two planesof metal atoms and pyrazolate linkers that mimic the planar CTC motif. The staggered confor-mation of the two planes results in reduced metallophilic interactions.NMNN NMM NN NMNN NMM NN NNHNNH HN N NHN41 42Chart 1.12: Structures of 41 and 42. M = Cu, Ag, Au. Ref.87Appropriate choice of pyrazole bridging linker and synthetic conditions gives metal-organicframeworks with cyclic trinuclear complexes as nodes. 3,3',5,5'-Tetramethyl-4,4'-bipyrazole(HBpz, 43) has been reacted with Cu+ 88,89 and Ag+ 89 in the presence of base to give 3D coor-191.3. Cyclic Trinuclear ComplexesNMNN NMM NN NMNN NMM NN NMNN NMM NN NMNNNMMNNN NHNHNHBpz (43) !-phase (44) "-phase (45)Chart 1.13: Structure of 43, 44, and 45. Ref.88,89dination polymers. The presence of a templating agent (mesitylene) generated a fourfold inter-penetrated ? phase (10,3)-a network (44) with 3.4 ? pores, accounting for the van der Waalsradii of the framework. An eightfold interpenetrated coordination polymer with no pores and a? phase (62?10)(6?102) topology (45) formed in the absence of a templating agent. Appreciablesurface areas and porosity were found for 44 and 45 and are attributed to the flexible nature ofthe frameworks. Chart 1.13 shows the difference interplanar and metallophilic coordination ofthe CTC units of 44 and 45. The macrocycles of 44 have a staggered geometry and the metalcenters of 45 are oriented in a chair geometry.Gold(I) 4-alkyl-3,5-dimethyl pyrazolate (46, alkyl = C7H15 ? C9H19, C11H23) cyclic trin-uclear complexes were investigated for their liquid crystalline properties.90 Complexes withheptyl and octyl groups formed hexagonal columnar mesophases, while CTCs with nonyl andundecyl groups exhibit only isotropic and crystalline phases. Notable of this system is thatonly three side chains per molecule are present. Scheme 1.7 shows the proposed transition incrystallographic unit cell dimensions between the elongated hexagonal crystalline phase andregular hexagonal mesophase of this class of compounds. Cyclic trinuclear complexes in thecrystalline phase form tilted dimeric pairs with two alkyl chains parallel to and four alkyl chainsperpendicular to the plane of the CTC, while the mesophase flattens the CTCs resulting in theformation of columnar stacks with the alkyl chains in an unknown orientation. Room temper-ature columnar mesophases were obtained from CTCs with decyloxyphenyl-pyrazole bridgingligands, which themselves are nonmesogenic.91 The authors note that there is a propensity forthese compounds to crystallize in near columnar orientations very close to those required toform columnar mesophases.201.3. Cyclic Trinuclear Complexes36.9 ? 33.8 ?19.5 ?11.4 ?Crystal Mesophaseac N NAuAuN NN Au NR RR C7H15C8H17C9H19C11H23R =46Scheme 1.7: Cell dimensions of the crystal and mesophase of 46. Adapted from Ref.90N NCuCuN NN Cu NR R'R'R R' R R  = CF 3 R' = HCF 3CF 3CF 3 CF 3Me Me PhMei-Pr i-Pr4 7 (a)(b) (c)(d)(e) (f)Chart 1.14: Structure of functionalized [3-R,5-R'-Cu(Pz)]3 (47) complexes. Ref.821.3.2 Electronic propertiesA seminal study of functionalized [3-R,5-R'-Cu(Pz)]3 complexes (47, Chart 1.14) by Omary82found that intramolecular copper-copper distances are insensitive to the electronic functionalityof the bridging pyrazolate but that bulkier substituents (e.g. phenyl) at the 3 and 5 positions ofthe linker will increase the intermolecular copper-copper separation distance. In solution, lu-minescence can depend both solvent concentration and identity, and dramatic thermochromismis observed in solution and in the solid state for compounds 47e and 47f. Photoinduced time-resolved single-crystal diffraction of 47d showed that the phosphorescent state is associatedwith the formation of a dimeric excimer pair instead of contracting intramolecular Cu?Cu dis-tances or the formation of a continuous polymeric chain of CTC units.92 The ground stateintermolecular Cu?Cu distances are 3.787 ? and 4.018 ?, while the excited state intermolec-ular Cu?Cu distances were found to be 4.05 ? and 3.46 ?: compression occurs between thelongest ground state intermolecular Cu?Cu contacts.Computational metrics such as centroid distance, planar distance, horizontal distance, androtational angle were varied to determine how structural variation influenced the electronics211.3. Cyclic Trinuclear ComplexesNNCuCu NN NCuNNN N=4 8 4 9Cu CuCu CNNC CN CNNC CN Cu CuCu Cu CuCu CNCN CN CNCN CNCN CNChart 1.15: Structure of complex 48 and coordination polymer 49. Ref.94of monomeric [M(Pz)]3 and dimeric {[M(Pz)]3}2 species of coinage metal pyrazolates.93 Thedimer participates in metallophilic interactions via the singlet ground state with a stabilizationenergy of 18.1 kcal mol?1 for copper(I) analogs. The T1 state is localized on gold(I) dimerscompared to the delocalized orbitals on the copper(I) and silver(I) dimers. Electronic groundstate metallophilic interactions are found to be quite weak, and large changes in geometry arepredicted to occur in the triplet excited state: when modeling dimeric CTCs, intermolecularcontraction was found to be much greater (average 20%) than intramolecular contraction (6%).As a consequence, the phosphorescent T1 ? S0 transition is expected to have a larger Stokesshift than for monomeric cyclic trinuclear systems.The electronic and structural properties of [Cu(Ppz)]3 (48) and coordination polymer {[Cu-(Ppz)]3[CuCN]3}n (49) (Ppz = 4-(pyrid-4'-yl)-3,5-dimethylpyrazolate) were investigated to de-termine the influence of an extended network on CTCs (Chart 1.15).94 Both compounds showthermochromic behavior. The rigid framework of 49 reduces the amount the CTC moietycan distort in the excited state, causing a hypsochromic shift in emission compared to 48. Thisblue-shift upon incorporation into a coordination polymer is opposite of what occurs for ligand-based luminescence in coordination polymers (see Section 1.2.3). A red-shift in ?em occurs in48 and 49 upon cooling to 150 K, while further cooling to 10 K causes the photoluminescencespectra to red-shift with ?em close to those found at room temperature. The change in emis-sion energy is larger for 48 than for 49 again due to the geometric constraints imposed by thecoordination polymer.Gold(I) 4-(3,5-dioctadecyloxybenzyl)-3,5-dimethylpyrazolate (50) was found to form a gelin hexane (Scheme 1.8) and exhibits ion and temperature-dependent photoluminescent prop-erties.81 The organogel luminescences red when excited with 284 nm light, while doping the221.4. Oligo- and PolythiophenesN NAuAuN NN Au N ORORORRO ORRO5 0 , R = C18H37 Hexane GelScheme 1.8: Gelation of 50. Adapted from Ref.81gel with Ag+ causes a blue luminescence when excited at 370 nm. Increasing the temperaturecauses the material to undergo a gel-sol transition. The Ag+-free sol has minimal lumines-cence intensity, whereas the Ag+ doped material is a green emitter. Luminescent propertieswere found to be reversible upon cooling-induced gelation or removal of Ag+. Lifetime mea-surements showed that all emitting states were long-lived (? = 3?6 ?s) and assigned to tripletexcited states. The authors hypothesize that the counterintuitive trend of an untreated gel hav-ing a higher HOMO-LUMO (HOMO = highest occupied molecular orbital, LUMO = lowestunoccupied molecular orbital) gap may be due to the distorted geometry of the triplet excitedstate since the ground state interactions are partially controlled by the alkyl chains.The ?-acidity and ?-basicity of coinage metal CTCs with bridging linkers carbenate, imi-dazolate, pyridinate, pyrazolate, or triazolate were modeled using density functional theory.95The authors found that the ?-acidity and HOMO-LUMO gaps of CTCs can be consistentlyand systematically tuned by varying the metal (relative ?-acidity Ag+ > Cu+ > Au+), organiclinker (relative ?-acidity triazolate > pyrazolate > carbenate > pyridinate > imidazolate), andsubstituents on the organic linker.1.4 Oligo- and PolythiophenesOligo- and polythiophenes are attractive candidates for electronic materials since function-alization, which is synthetically accessible, leads to changes in the electronic properties96with-out drastically changing conductivity,97 and they are often air-stable compounds that can be231.4. Oligo- and PolythiophenesS S S2 -2e- S H SH-2H+S S-e-S SS S-2(n-2)H+n-2n!""!Scheme 1.9: Electropolymerization of thiophene.characterized using common instruments. Functionality can be added to oligothiophenes suchthat they can coordinate to transition metal centers, or the thiophene can readily coordinatethrough the lone pair on the sulfur atom and in ?2, ?4, or ?5 fashions.98 ?-Linkages extendthe conjugation lengths, while minimal electronic communication occurs between ?-linkedthienyl units.99 Oligo- and polythiophenes are synthesized from transition metal catalyzedcross-coupling reactions, cyclization reactions, and chemical and electrochemical oxidativecouplings.100 In addition, defects often occur during the synthesis of oligo- and polythiophenesincluding oxidation and ?-? linkage isomerization.99Thin film polythiophenes can be grown directly onto a substrate by the electrochemicalcoupling mechanism described in Scheme 1.9. Electrochemical coupling relies on an oxida-tive potential to remove an electron from the ?-position of a thiophene ring. Two thiopheneradical cations can react to form a bithiophene dication dimer, and elimination of 2H+ givesbithiophene. Subsequent oxidations will be lower in potential as the oligothiophene increasesin length. Unfortunately, irreversible over-oxidation of oligothiophenes occurs more readilyas the conjugation length increases, and this irreversible oxidation changes the photophysicaland conductive properties of the polymer.101 This phenomenon, known as the ?polythiopheneparadox,? is one disadvantage of electropolymerization.Figure 1.6 shows a qualitative energy level diagram of oligothiophenes of increasing con-jugation length, and this example can be applied to other conjugated materials. Increasingthe conjugation length decreases the redox potential and HOMO-LUMO energy gap of theoligomer, thereby causing a red shift both absorption and photoluminescence. Electron donat-ing and withdrawing groups as well as varying the dihedral angle between thiophenes can tunethe HOMO-LUMO gap of oligothiophenes. An oligothiophene with smaller annular torsionangles should be more conjugated and undergo bathochromic shifts in electronic transitions241.4. Oligo- and Polythiophenescompared to the same oligothiophene with near perpendicular torsion angles.Sn=1 n=2 n=3 nEnergy n ? Conduction BandValence BandLUMOHOMO Band GapIncreasing conjugationFigure 1.6: Qualitative energy level diagram for oligo- and polythiophenes.Oligothiophenes have been found to crystallize in parallel fashion with alternating molecu-lar planes between 35? and 62? and often in a herringbone orientation (having molecular planesof 60?).102 Sulfur-sulfur contact distances range between 3.6 ? and 3.9 ?. Longer chain olig-othiophenes are more planar than shorter chain oligothiophenes: crystalline terthiophene ex-hibits thienyl torsion angles between 6? and 9?, while dihedral torsion angles of sexithiophenedeviate less than 1? from planarity.103 Complexation of Li+, Na+, and K+ with crown etherside chains appended to polythiophene results in ionochromic responses which are caused byconformational perturbations of the thienyl backbone.104Interchain organization of polythiophenes is influenced by pressure, temperature, and sol-vent. Pressure studies of poly(3-hexylthiophene) (P3HT) (51, Chart 1.16) showed that thepolymer undergoes two transitions when exposed to increasing pressures, and these changeswere monitored by UV-Vis absorption and conductivity measurements.105 Initially, the com-pact packing of the alkyl chains is thought to planarize the polymer chains. Beyond pressuresof 3 GPa, the benefits of compact packing give way to interchain steric hindrance. Additionof acetonitrile into a chloroform solution of P3HT followed by spin-coating thin films trans-forms the polymer from a random coil orientation to ordered nanocrystals.106 When these filmsare incorporated into field-effect transistors, an enhanced field-effect mobility was found in theacetonitrile-doped samples. Thermochromism is observed in P3HT films; at room temperature,an absorption band is present at 2.5 eV, while heating of the film causes the growth of a band251.5. Goals and Scope of ThesisSC6H13n51 S S SS C14H29C14H29 n52Chart 1.16: Structure of 51 and 52. Ref.105,107near 3 eV along with the attenuation of the band at 2.5 eV.105 The band at 2.5 eV is assigned toa planar conformation of P3HT, and the heating-induced band near 3 eV belongs to a twistedconformation. Thin films of poly(2,5-bis(3-quaterdecylthiophen-2-yl)thieno[3,2-b]thiophene)(52) have improved charge mobility, more conjugated backbones, and are highly ordered afterheating through a thermotropic mesophase.107 Cooling of 52 gives a crystalline material wherethe order and enhanced properties obtained in the mesophase are maintained.Crystallographically characterized mercury(II) thienyl (53) and bithienyl (54) complexeswere found to form weak 3D and 2D coordination networks via weak non-covalent Hg ? ? ? Hgcontacts of 3.94 ? and 3.85 ?, respectively.108 Figure 1.7 shows the extended structure ofthese compounds with the Hg ? ? ? Hg contacts highlighted in red. Intermolecular electrostaticinteractions cause twisting of the bithienyl moieties which have an annular torsion angle of26.7?. Hg ? ? ? S contacts (3.752 ?) are attributed to electron density donated from the sulfurlone pair to an unoccupied orbital on mercury.1.5 Goals and Scope of ThesisThe main goal of this thesis is to explore how the orientation of oligothiophene deriva-tives influence the structural, electronic, and magnetic properties of coordination polymers andcyclic trinuclear complexes. Intermolecular interactions and annular torsion angles of oligoth-iophenes will be discussed. Chapter 2 investigates the influence of co-ligands and oligothio-phene functionalization on the solid state molecular structure, absorption, photoluminescence,and thermal stability of coordination polymers. Additionally, the impact of reaction condi-tions on the synthesis of coordination polymers will be discussed. Structural information frompowder X-ray diffraction patterns will be elucidated. Chapter 3 further explores the struc-tural diversity of functionalized bithiophene and terthiophene coordination polymers. A seriescrystallographically characterized terthiophene coordination polymers is expanded upon, anddifferences in the syntheses and structures of these compounds will be examined. The mag-261.5. Goals and Scope of Thesisa)b)Figure 1.7: Extended structures of a) 53; b) 54. Hg ? ? ? Hg contacts are shown in red. C: black.S: yellow. Hg: gray. Adapted from Ref.108netic properties of manganese frameworks are discussed, and relations between structure andmagnetic behavior are drawn. Chapter 4 evaluates the influence of thienyl moieties on gold(I)pyrazolate cyclic trinuclear complexes. Structural modifications to the bridging thienyl pyra-zolate such as including substituents that will change the thienyl pyrazole torsion angle andhaving aryl and biaryl groups at the 4-position of pyrazole will be explored with respect toaurophilic interactions and thermoluminescence. Computational studies were performed toconfirm theories drawn from experimental observations, in particular how the extent of ligandconjugation tunes the nature of the cyclic trinuclear complex excited state. The cyclic voltam-metry and electropolymerization of thin films of cyclic trinuclear complexes will be presented.27Chapter 2Luminescent Coordination Polymers2.1 IntroductionIncorporating oligothiophenes into crystalline coordination polymers is a method for an-alyzing extended systems without the usual defects that are prevalent in solution-based poly-meric systems. For example, synthetic contaminants can provide quenching sites, and defectsin connectivity can arise during polymer synthesis.109,110 The optoelectronic properties andbandgap of oligo- and polythiophenes, as well as their coordination polymers, depends on theextent of conjugation.100 Consequently, the degree of conjugation and amount of orbital over-lap will depend on the planarity of the oligomer or polymer. Annular torsion angle is a metricused to quantify the degree of planarity and is data that can be determined through theoreticalcalculations or from crystallographic data.Controlling the degree of planarity is relevant to applications such as thermochromismin both solution and the solid state. Theoretical work has shown a balance of repulsive in-tramolecular interactions, attractive intermolecular forces, and the identity of the substituentcontribute whether or not temperature-dependent changes in planarity and electronic structureoccur within polythiophenes.111 Thermochromism is observed in 3,3'-substituted poly(2,2'-bithiophene)s while thermochromism is not observed in the cases of poly(3,3'-dialkoxy-2,2'-bithiophene)s and poly(3-alkoxythiophene)s. The non-thermochromic polymers have beenfound to be coplanar when isolated and as aggregates, whereas poly(3,3'-dialkyl-2,2'-bithio-phene)s are found to not be co-planar in the solid state due to large repulsive forces. On theother hand, poly(3,3'-di(alkylthio)-2,2'-bithiophene)s do exhibit changes in annular torsion an-gle with varying temperature.111Coordination of a functionalized oligothiophene to a metal can aid in the crystallizationof the oligomer with various annular torsion angles and in different orientations. Crystallo-graphically characterized coordination polymers can help to correlate ligand and metal-ligandstructure with emission behavior. Lanthanides and transition metals without unpaired electrons(particularly d10 metals Zn(II) and Cd(II)) are good candidates to incorporate into metal centersof coordination polymers. While lanthanides provide a broader coordination sphere compared282.1. Introductionto d10 metals as well as a variety of emission pathways (e.g. metal-based emission, ligand? ? ?* emission, and ligand ? to ligand-metal ??), extended conjugation lengths of the ligandwill quench lanthanide-based emission (Figure 1.3).40Thiophene derivatives have been a popular choice for studying the structure and lumines-cent properties of solid state coordination polymers. Most examples of thiophene-containingcoordination polymers use thiophene-2,5-dicarboxylic acid (H2TDC, 55) as a linker112?120 dueto its non-colinear linking angle of 151? and its use as an intermediate for the synthesis ofa fluorescent brightening reagent.113 Thiophene-2,5-dicarboxylate is often coordinated to lan-thanides since the linker excited state often lies above the LUMO of the metal and does notquench metal-based emission (vida supra).Reaction of 4,4'-bpy and H2TDCwith Fe3+, Co2+, Zn2+, or Cd2+ gives isostructural two-foldinterpenetrated 3D coordination polymers [M2+TDC(4,4'-bpy)]n (56) where the TDC2? linkerforms 2D sheets and the 4,4'-bpy forms doubly pillared struts (Chart 2.1).120,121 Carboxylategroups bridge the octahedral metal centers to form binuclear clusters. Reduction of Fe3+ to Fe2+occurs under hydrothermal conditions in the presence of 4,4'-bpy.122 Very recently Kettner andco-workers have discovered [Co(TDC)(4,4'-bpy)]n can catalytically oxidize cyclooctene (inthe presence of tert-butyl hydroperoxide) more effectively than Basolite C300, a commerciallyavailable Cu2+-based coordination polymer.121S CO2O2C M OO OO NN M OO OO NNNNN NO O = 5 5 , H2TDC 5 6Chart 2.1: Structure of thiophene linker H2TDC (55) and metal-organic framework [M2+TDC-(4,4'-bpy)]n (56). Adapted from Ref.120Ionothermal synthesis in deep eutectic solvents including choline chloride and ethyleneureahemihydrate has been employed to produce a series of lanthanide thiophene coordination poly-292.1. Introductionmers.113 In this series of compounds, H2TDC was found to be a good sensitizer for lanthanideion emission, especially for Eu3+. In the case of Nd3+, an intense blue emission was assignedas ?-ligand to ?*-Nd?O. The difference between the Eu3+ and Nd3+ systems highlights theimportance of where the ligand triplet lies with respect to the metal excited state and groundstate.Thiophene covalent-organic frameworks (COFs) have been synthesized by the condensa-tion of 2,3,6,7,10,11-hexahydroxytriphenylene (57, HHTP) with thiophene (58), bithiophene(59), and thieno[3,2-b]thiophene (60) diboronic acids (Chart 2.2) to give stacked 2D latticesthat form 1D interlayer columns.123 Synthesis of these COFs was not straightforward, and theauthors credit this to the defect-prone bent diboronic acids used. The off-white microcrys-talline powder made from HHTP and 60 can be doped with electron acceptor tetracyanoquin-odimethane (TCNQ, 61) to form a black charge transfer complex with absorption centered at850 nm. OHOHHOHO OH OHS B(OH) 2(HO) 2B S(HO) 2B S(HO) 2B S B(OH) 2S B(OH) 2 CNNC CNNC61, TCNQ57, HHTP605958Chart 2.2: Structure of 57?61. Ref.1232,2'-Bithiophene 5,5'-dicarboxylic acid (H2T2DC, 62) has been reacted with first row tran-sition metal salts of Zn2+, Co2+, and Mn2+ under solvothermal conditions to give isostruc-tural 1D coordination polymers (Zn2+ and Co2+) and a 3D network (Mn2+) comprised of6-connected trinuclear centers.124 The Zn2+ analog, which has has a molecular formula of[Zn(T2DC)(DMF)2 ? DMF]n (71), was synthesized and crystallographically characterized priorto the publication of the findings of Li and co-workers. The authors claimed a qualitative en-hancement of fluorescence intensity upon coordination of H2T2DC to Zn2+ while fluorescencequenching was observed for species coordinated to paramagnetic Co2+ and Mn2+ centers.302.1. IntroductionA mixed linker system was synthesized and crystallographically characterized success-fully in our lab shortly before Kitagawa?s publication of two isomers of the same compound,[ZnT2DC(4,4'-bpy)0.5]n (76).125 As shown in Figure 2.1, one structure is a rigid three-fold in-terpenetrated framework formed under homogeneous conditions, while the other is a twofoldinterpenetrated flexible framework that forms under inhomogeneous conditions or in the pres-ence of a non-binding additive such as benzene (see Figure A.1a for metal center coordination).Both frameworks show the ability to adsorb CO2 at 195 K, and the more flexible material isable to store four times more molecules of CO2 per formula unit than its rigid analog.Figure 2.1: Extended structure of the rigid (left) and flexible (right) isomers of [Zn(T2DC)-(4,4'-bpy)0.5]n (76). Adapted from Ref.125Extension of the thiophene oligomer length to three units gives 2,2':5',2''-terthiophene-5,5''-dicarboxylic acid (H2T3DC, 63) which has the ability to coordinate in cis,cis, cis,trans,or trans,trans orientations. Beyond this work, examples of crystallographically characterizedterthiophene coordination polymers have not been reported, although palladium(II) complexesof phosphinoterthiophene ligands have been electropolymerized to create conductive thin filmsof terthiophene-containing coordination polymers.126 A Cu2+-terthiophene metal-organic poly-hedron (64, Chart 2.3) comprised of six binuclear paddlewheel subunits and 12 cis,cis-T3DC2?that have a linking angle close to 90? was synthesized by Yaghi and co-workers.127 The macro-molecule adopts a truncated octahedron shape and exhibited a surface area and porosity similarto extended coordination polymers. The T3DC2? units are fairly planar with thienyl dihedralangles ranging between -0.6(6)? and 12.7(5)?.312.2. ExperimentalS S S CO2O2C OOOOOO OOCuCuH2OO N== 6463Chart 2.3: Structure of 63 and 64. Ref.127With these structural and functional considerations in mind, expansion of the series of olig-othiophene dicarboxylic acids will help to realize new conformations of oligothiophenes inthe solid state as well as the corresponding photophysical properties. In addition to H2T2DCand H2T3DC, phenyl and n-hexyl functional groups were appended to the ?-position of theoligothiophenes to vary the structural and electronic properties of the subsequent coordinationpolymers. Bis(thienyl)benzene derivatives may provide structural analogs to terthiophene link-ers but with blue shifted emission profiles. N-heterocyclic co-linkers were incorporated intocoordination polymers to provide structural variety. Appropriate choice of a co-linker mayfacilitate an energy transfer mechanism or other perturbation of photoluminescence.2.2 Experimental2.2.1 GeneralZn(NO3)2? 6 H2O, 4,4'-bipyridine (4,4'-bpy, 65), trans-1,2-bis(4-pyridyl)ethylene (bpe, 66),and n-butyllithium were purchased from Sigma-Aldrich. Deuterated solvents were purchasedfrom Cambridge Isotope Laboratories. Dimethylsulfoxide (DMSO) and N,N-dimethylform-amide (DMF) were purchased from Fisher Scientific. N,N-Diethylformamide (DEF) was pur-chased from TCI America. All chemicals were used as received. 2,2'-Bithiophene-5,5'-di-carboxylic acid (H2T2DC, 62),125 and 2,2':5',2''-terthiophene-5,5''-dicarboxylic acid (H2T3DC,322.2. Experimental63)127 were synthesized according to literature procedures.THF was distilled from Na/benzophenone. 1H and 13C NMR spectra were collected on aBruker AV-300 or AV-400 spectrometer and were referenced to residual solvent signals: d6-DMSO, 2.50 ppm (1H), 39.5 ppm (13C); CD3OD, 3.31 ppm (1H), 49.0 ppm (13C). UV-Visabsorption and diffuse reflectance spectra were collected using a Cary 5000 spectrometer. AHarrick Praying Mantis accessory was used to collect diffuse reflectance spectra of solid sam-ples. Emission and excitation spectra were obtained on a Photon Technology International flu-orimeter using a 75-W arc lamp as a source and were uncorrected for lamp intensity. EI massspectra were obtained using a Kratos MS-50 mass spectrometer coupled to a MASPEC datasystem. Infrared spectra were obtained on a Thermo Nicolet 6700 with a Smart Orbit acces-sory in the range of 4000-400 cm?1. CHN elemental analysis was performed using a EA1108elemental analyzer. Thermogravimetric analyses (TGA) were performed using a Perkin ElmerPyris 6 Thermogravimentric Analyzer under a nitrogen atmosphere at a rate of 10? min?1. Pow-der X-ray diffraction (PXRD) scans were performed on a Bruker D8 Advance instrument withgraphite monochromated Cu-K? radiation at a scan rate of 5? min?1 for 71?82 and 1.2? min?1for compounds 83?85.2.2.2 Procedures3,3'-Diphenyl-2,2'-bithiophene-5,5'-dicarboxylic acid (H23PhT2DC, 67):THF (35 mL) was added to a round bottom flask with a side-arm charged with 3,3'-diphenyl-2,2'-bithiophene128 (1.12 g, 3.51 mmol). The flask was cooled to -78 ?C and n-butyllithium(4.6 mL, 7.3 mmol, 1.6 M in hexanes) was added dropwise. The initially colorless solutionturned slightly yellow-green during the addition. The reaction was first warmed to then held at0 ?C for one hour, then cooled back to -78 ?C. Excess solid carbon dioxide pellets were added,resulting in the formation of an off-white opaque suspension. The flask was allowed to warmto room temperature overnight. Water (30 mL) was then added to quench the reaction. Theaqueous layer was washed with diethyl ether (3 ? 15 mL), and the product was precipitatedby the addition of excess 1 M HCl, filtered, washed with 0.1 M HCl, methanol, and diethylether, and finally dried in vacuo to afford a white solid (1.3 g, 91 % yield). m/z: 406. MP >300 ?C. 1H NMR (300 MHz, DMSO-d6): ? 7.74 (s, 2H), 7.24 (m, 6H), 7.10 (m, 4H). 13C NMR(75.5 MHz, DMSO-d6): ? 162.3, 142.11, 135.3, 134.4, 134.2, 134.0, 128.4, 128.1, 127.6. FT-IR (cm?1): 3029 (m, br), 2618 (m, br), 1670 (s), 1536 (m), 1496 (m), 1425 (s), 1260 (m, br),1208 (s), 872 (w), 750 (s), 692 (s), 493 (m, br), Elem Calcd for C22H14O4S2: C, 65.01; H, 3.47;332.2. ExperimentalFound: C, 65.28; H, 3.65.3,3'-Dihexyl-2,2'-bithiophene-5,5'-dicarboxylic acid (H23HT2DC, 68):3,3'-Dihexyl-2,2'-bithiophene129 (0.985 g, 2.94 mmol) was added to THF (30 mL). Theflask was cooled to -78 ?C and n-butyllithium (4.0 mL, 6.4 mmol, 1.6 M in hexanes) wasadded dropwise. The initially colorless solution turned slightly yellow during the addition.The reaction mixture was warmed to and held at 0 ?C for one hour, then cooled to -78 ?C. Ad-dition of excess solid carbon dioxide pellets resulted in the formation of a light yellow opaquesuspension. The reaction was allowed to warm to room temperature overnight. Water (25 mL)was then added to quench the reaction. The aqueous layer was washed with diethyl ether(3 ? 15 mL), and the product was precipitated by the addition of excess 1 M HCl, filtered,washed with 0.1 M HCl, water, and finally dried in vacuo to afford an off-yellow solid (1.1 g,87 % yield). m/z: 422. MP: 162 ?C. 1H NMR (CD3OD): ? 7.68 (s, 2 H); 2.54 (t, J = 8 Hz, 4 H);1.57 (m, 4 H); 1.25 (m, 12 H); 0.86 (t, J = 7 Hz, 6 H). 13C NMR (75.5 MHz, CD3OD): ? 164.9,145.3, 136.0, 135.8, 130.8, 32.7, 31.6, 30.1, 29.9, 23.7, 14.6. FT-IR (cm?1): 2992 (m), 2853(m), 2561 (w, br), 1662 (vs), 1525 (s), 1421 (s), 1271 (s), 1194 (s), 863 (m), 750 (m), 714 (m),497 (m). Elem Calcd for C22H30O4S2: C, 62.53; H, 7.16. Found: C, 62.60; H, 7.12.1,4-Di(5-carboxythiophen-2-yl)benzene (H2TPhTDC, 69)1,4-Bis(2-thienyl)benzene130 (0.969 g, 4.00 mmol) was added to THF (35 mL). The flaskwas cooled to 78 ?C and n-butyllithium (5.2 mL, 8.4 mmol, 1.6 M in hexanes) was addeddropwise. The initially colorless solution turned yellow then orange during the addition. Thereaction mixture was warmed to 0 ?C and maintained at this temperature for one hour, thencooled to -78 ?C. Addition of excess solid carbon dioxide pellets resulted in the formation ofa light yellow opaque suspension. The reaction was allowed to warm to room temperatureovernight. Water (25 mL) was then added to quench the reaction. The aqueous layer waswashed with diethyl ether (3 ? 15 mL), and the product was precipitated by the addition ofexcess 1 M HCl, filtered, washed with 0.1 M HCl, methanol, diethyl ether, and finally driedin vacuo to afford a yellow solid (1.2 g, 89 % yield). m/z: 330. MP: > 300 ?C. 1H NMR(400 MHz, DMSO-d6) ? 7.82 (s, 4 H); 7.73 (d, J = 4 Hz, 2 H); 7.63 (d, J = 4 Hz, 2 H). 13CNMR (100 MHz, DMSO-d6): ? 164.3, 141.9, 133.1, 128.9, 126.2, 125.8, 124.2. FT-IR (cm?1):3031 (w, br), 2862 (w, br), 1666 (vs), 1539 (m) 1514 (w), 1497 (w), 1438 (s). 1305 (m), 1280(m), 1200 (m), 1105 (w), 1071 (w), 1026 (w), 915 (m), 878 (m), 834 (m), 752 (s), 707 (w),342.2. Experimental695 (s), 682 (m), 629 (m), 588 (w), 505 (m), 480 (m). Elem Calcd for C16H10O4S2: C, 58.17;H, 3.05. Found: C, 58.52; H, 3.21.3',4'-Diphenyl-2,2':5',2''-terthiophene-5,5''-dicarboxylic acid (H2Ph2T3DC, 70):3',4'-Diphenyl-2,2':5',2''-terthiophene128 (0.41 g, 1.0 mmol) was added to THF (20 mL).The flask was cooled to -78 ?C and n-butyllithium (1.3 mL, 2.1 mmol, 1.6 M in hexanes) wasadded dropwise. The yellow solution turned yellow-orange, then green during the addition.The reaction mixture was warmed to and held at 0 ?C for one hour, then cooled to -78 ?C.Addition of excess solid carbon dioxide pellets resulted in the formation of a vibrant orangeopaque suspension. The reaction was allowed to warm to room temperature overnight. Water(20 mL) was added to quench the reaction. The aqueous layer was washed with diethyl ether(3 ? 10 mL), and the product was precipitated by the addition of excess 1 M HCl, filtered,washed with 0.1 M HCl, methanol, diethyl ether, and finally dried in vacuo to afford an orangesolid (0.42 g, 86 % yield). m/z: 488. MP > 300 ?C. 1H NMR (400 MHz, DMSO-d6) ? 7.56(d, J = 3.9 Hz, 2 H), 7.29 (m, 6 H), 7.18 (m, 6 H). 13C NMR (100 MHz, DMSO-d6): ? 162.5,134.5, 133.0, 131.8, 130.8, 130.2, 128.5, 128.3, 126.9, 125.1, 117.1. FT-IR (cm?1) 3390 (w,br), 3052 (w) 2809 (w), 2521 (w, br), 1651 (s), 1513 (m), 1487 (w), 1440 (s), 1289 (m, br),1112 (m), 1050 (w), 917 (w), 797 (m), 745 (m), 699 (s), 623 (w), 511 (m), 483 (w), ElemCalcd for C26H16O4S3: C, 63.91; H, 3.30; Found C, 63.46; H, 3.23.[Zn(T2DC)(DMF)2 ? DMF]n (71):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol) and 62 (25 mg, 0.10 mmol) were dissolved in DMF(3 mL). The solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed. The ves-sel was heated to and held at 110 ?C for 24 hours, and then the bomb was cooled at a rate of3.7 ?C hr?1. Colorless crystals of 71 were isolated in 85 % yield. FT-IR (cm?1): 3271 (m),3109 (m), 1651 (w), 1538 (m), 1519 (s), 1431 (m), 1367 (s), 1289 (m), 1119 (m), 1053 (m),906 (w), 890 (w), 833 (m), 806 (m), 763 (s), 661 (m), 578 (w), 552 (m), 414 (m). Elem Calcdfor C19H25N3O7S2Zn: C, 42.50; H, 4.69; N, 7.83. Found C, 42.43; H, 5.01; N, 7.58.[Zn(T2DC)(DEF)2]n (72):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol) and 62 (25 mg, 0.10 mmol) were dissolved in DEF(3 mL). The solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed. The ves-352.2. Experimentalsel was heated to and held at 110 ?C for 24 hours, and then the bomb was cooled at a rate of3.7 ?C hr?1. Colorless crystals of 72 were isolated in 57 % yield. FT-IR (cm?1): 3088 (w),2981 (w), 2943 (w), 1645 (w), 1625 (m), 1589 (w), 1517 (m), 1435 (s), 1360 (s), 1270 (m),1210 (m), 1191 (w), 1107 (m), 1035 (m), 947 (w), 884 (w), 814 (m), 773 (s), 662 (m), 648(m), 520 (w), 439 (m). Elem Calcd for C20H26N2O6S2Zn: C, 46.20; H, 5.04; N, 5.39; FoundC, 46.92; H, 4.89; N, 4.96.[Zn(T2DC)(DMSO)2 ? DMSO]n (73):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol) and 62 (25 mg, 0.10 mmol) were dissolved inDMSO (3 mL). The solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed.The vessel was heated to and held at 110 ?C for 24 hours, and then the bomb was cooled at arate of 3.7 ?C hr?1. Colorless crystals of 73 were isolated in 44 % yield. FT-IR (cm?1): 3073(w, br), 1521 (m), 1507 (s), 1437 (m), 1342 (m), 1289 (m), 1174 (w), 1133 (vs), 1127 (m),1076 (s), 890 (w), 835 (m), 814 (m), 777 (s), 667 (m), 589 (w), 571 (m), 503 (m), 453 (w).Elem Calcd for C16H22O7S5Zn: C, 34.81; H, 4.02. Found: C, 35.63; H, 4.58.[Zn2(3PhT2DC)2(DMA)2 ? 3 DMF]n (74):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol) and 67 (41 mg, 0.10 mmol) were dissolved in DMF(5 mL). The solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed. The ves-sel was heated to and held at 110 ?C for 24 hours, and then the bomb was cooled at a rate of3.7 ?C hr?1. Colorless crystals of 74 were isolated in 64 % yield. FT-IR (cm?1): 3258 (w), 3056(w, br), 1626 (s), 1540 (m), 1422 (s), 1381 (s), 1355 (s), 1213 (m), 1122 (m), 1025 (m), 899(w), 800 (s), 775 (m), 713 (m), 691 (s), 633 (m), 428 (m). Elem Calcd for C57H59N5O11S4Zn2:C, 54.81; H, 4.76; N, 5.61. Found: C, 55.36; H, 4.73; N, 5.30.[Zn(3HT2DC)(DMA)]n (75):Zn(NO3)2? 6 H2O (59 mg, 0.20 mmol) and 68 (42 mg, 0.10 mmol) were dissolved in DMF(6 mL). The colorless solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed.The vessel was heated to and held at 110 ?C for 24 hours, and then the bomb was cooled at arate of 3.7 ?C hr?1. Colorless crystals of 75 were isolated in 52 % yield. FT-IR (cm?1): 3282(w), 2925 (m), 2852 (m), 1623 (s), 1538 (m), 1426 (s), 1394 (s), 1362 (s), 1199 (w), 1024 (w),904 (w), 799 (w), 773 (s), 714 (m), 454 (m, br). Elem Calcd for C24H34NO4S2Zn: C, 52.69; H,362.2. Experimental6.45; N, 2.56. Found: C, 52.92; H, 6.85; N, 2.32.[Zn(T2DC)(4,4'-bpy)0.5]n (76):Zn(NO3)2? 6 H2O (59 mg, 0.20 mmol), 62 (25 mg, 0.10 mmol), and 65 (16 mg, 0.10 mmol)were dissolved in DMF (6 mL). The colorless solution was transferred to a 23 mL Teflon-linedParr bomb and sealed. The vessel was heated to and held at 110 ?C for 24 hours, and thenthe bomb was cooled at a rate of 3.7 ?C hr?1. Colorless crystals of 76 were isolated in 68 %yield. FT-IR (cm?1): 1667 (m), 1621 (m), 1519 (m), 1428 (s), 1378 (vs), 1320 (m), 1254 (m),1218 (m), 1071 (m), 1039 (m), 888 (w), 809 (m), 767 (s), 696 (w), 647 (m) 569 (w), 451 (m).Elem Calcd for C15H8NO4S2Zn: C, 45.53; H, 2.04; N, 3.54. Found: C, 44.91; H, 2.47; N, 4.29.[Zn(3PhT2DC)(4,4'-bpy)0.5(DMF) ? DMF ? H2O]n (77):Zn(NO3)2? 6 H2O (59 mg, 0.20 mmol), 67 (41 mg, 0.10 mmol), and 65 (16 mg, 0.10 mmol)were dissolved in DMF (6 mL). The colorless solution was left at room temperature in a cappedvial. Colorless crystals of 77 formed after two weeks and were isolated in 36 % yield. FT-IR(cm?1): 2962 (w), 1668 (s), 1591 (m), 1533 (m), 1495 (w), 1409 (s), 1372 (s), 1351 (s), 1213(m), 1091 (m), 1026 (w), 875 (w), 805 (s), 760 (m), 695 (m), 626 (m), 501 (m), 466 (w). ElemCalcd for C33H30N3O7S2Zn: C, 55.82; H, 4.26; N, 5.92. Found: C, 54.40; H, 5.19; N, 4.44.[Zn(3HT2DC)(4,4'-bpy)0.5]n (78):Zn(NO3)2? 6 H2O (59 mg, 0.20 mmol), 68 (42 mg, 0.10 mmol), and 65 (16 mg, 0.10 mmol)were dissolved in DMF (6 mL). The colorless solution was left at room temperature in a cappedvial and colorless crystals of 78 formed after two weeks and isolated in 31% yield. FT-IR(cm?1): 2962 (w), 2924 (m), 2854 (m), 1667 (w), 1613 (m), 1538 (m), 1491 (w), 1426 (s),1392 (s), 1360 (s), 1220 (w), 1195 (w), 1073 (w), 1018 (w), 870 (w), 812 (m), 801 (w), 773(s), 726 (m), 645 (m), 570 (w), 462 (m). Elem Calcd for C27H32NO4S2Zn: C, 57.49; H, 5.72;N, 2.48. Found: C, 58.38; H, 6.29; N, 2.14.[Zn(T2DC)(bpe)0.5]n (79):Zn(NO3)2 ? 6 H2O (30 mg, 0.10 mmol), 62 (13 mg, 0.050 mmol), and 66 (9 mg, 0.05 mmol)were dissolved in DMF (5 mL). The colorless solution was transferred to a 23 mL Teflon-lined372.2. ExperimentalParr bomb and sealed. The vessel was heated to and held at 110 ?C for 24 hours, and then thebomb was cooled at a rate of 3.7 ?C hr?1. Yellow crystals of 79 were isolated in 72 % yield.FT-IR (cm?1): 1614 (m), 1519 (m), 1431 (m), 1379 (s, br), 1075 (w), 1033 (m), 953 (w), 820(w), 798 (w), 766 (s), 652 (w), 550 (m), 446 (m, br). Elem Calcd for C16H9NO4S2Zn: C, 47.01;H, 2.22; N, 3.43. Found C, 46.68; H, 2.59; N. 3.37.[Zn(3PhT2DC)(bpe) ? 2 DMF]n (80):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol), 67 (41 mg, 0.10 mmol), and 66 (18 mg, 0.10 mmol)were dissolved in DMF (6 mL). The light yellow solution was left at room temperature in acapped vial and light yellow crystals of 80 formed after two days and were isolated in 42 %yield. FT-IR (cm?1): 1611 (s), 1537 (m), 1497 (m), 1425 (s), 1365 (s), 1350 (s), 1210 (m),1028 (m), 834 (m), 754 (s), 691 (s), 570 (s), 518 (w), 406 (w). Calcd C40H36N4O6S2Zn, C,60.19.; H, 4.54; N, 7.01. Found C, 60.34; H, 4.07; N, 6.53.[Zn3(3HT2DC)3(bpe)2 ? 4 DMF ? H2O]n (81):Zn(NO3)2 ? 6 H2O (30 mg, 0.10 mmol), 68 (21 mg, 0.050 mmol), and 66 (9 mg, 0.05 mmol)were dissolved in DMF (4 mL). The light yellow solution was left at room temperature in acapped vial. Light yellow crystals of 81 formed after three days and were isolated in 27 %yield. FT-IR (cm?1): 2925 (m), 2854 (m), 1597 (s), 1532 (m), 1421 (s), 1390 (s), 1351 (s),1195 (w), 1101 (w), 1030 (w), 957 (w), 827 (w), 799 (w), 772 (m), 717 (w), 551 (m), 420 (w,br). Elem Calc for C102H134N8O17S6Zn3: C, 57.44; H, 6.33; N, 5.25; Found C, 58.49; H, 5.59;N, 3.04.1[Zn0.5(TPhTDC)0.5(DMF) ? DMF]n (82):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol) and 69 (33 mg , 0.10 mmol) were dissolved in DMF(10 mL). The yellow solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed.The vessel was heated to and held at 110 ?C for 24 hours, and then the bomb was cooled at arate of 3.7 ?C hr?1. Yellow crystals suitable for SCXRD were isolated in 71 % yield. FT-IR(cm?1): 1660 (m), 1651 (s), 1593 (m), 1543 (m), 1506 (w), 1447 (m), 1359 (s), 1252 (m), 1114(m), 1089 (m), 1062 (w), 1045 (m), 957 (w), 867 (w), 820 (m), 808 (m), 774 (s), 693 (m), 6601Elemental analysis of 81 corresponds to the solvent-free material calculated for solvent-free[Zn3(3HT2DC)3(bpe)2]n: C, 59.32; H, 5.75; N, 3.07.382.2. Experimental(m), 595 (w), 532 (m), 472 (m), 423 (w). Elem Calcd for C14H18N2O4SZn0.5: C, 49.02; H,5.29; N, 8.17. Found: C, 48.62; H, 4.77; N, 7.36.[Zn(T3DC) ? x DMF ? y H2O]n (83):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol) and 63 (34 mg, 0.10 mmol) were dissolved in DMF(15 mL). The orange solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed.The vessel was heated to and held at 110 ?C for 24 hours, and then the bomb was cooled at arate of 3.7 ?C hr?1. A red-orange powder was isolated in 73 % yield (based on formula deter-mined from elemental analysis). FT-IR (cm?1): 3604 (m), 1660 (m), 1568 (s), 1531 (w), 1508(m), 1441 (s), 1380 (s, br), 1129 (m), 1058 (w), 1034 (m), 797 (m), 766 (s), 656 (m), 637 (m),480 (m), 458 (m), 402 (m). Elem Found: C, 33.53; H, 2.98; N, 3.96.[Zn(T3DC)(4,4'-bpy) ? x DMF ? y H2O]n (84):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol), 63 (34 mg, 0.10 mmol), and 65 (16 mg, 0.10 mmol)were dissolved in DMF (15 mL). The orange solution was transferred to a 23 mL Teflon-linedParr bomb and sealed. The vessel was heated to and held at 110 ?C for 24 hours, and then thebomb was cooled at a rate of 3.7 ?C hr?1. A light orange powder was isolated in 67 % yield(based on formula determined from elemental analysis). FT-IR (cm?1): 3076 (w), 2916 (w),1674 (s), 1605 (w), 1591 (m), 1512 (m), 1447 (m), 1383 (s), 1325 (w), 1258 (w), 1218 (m),1066 (m), 1045 (w), 864 (m), 818 (s), 798 (w), 764 (m), 730 (w), 632 (m), 538 (w), 475 (m).Elem Found: C, 50.53; H, 3.34; N, 6.13.[Zn2(Ph2T3DC)2(DMF)4(H2O)]n (85):Zn(NO3)2 ? 6 H2O (59 mg, 0.20 mmol) and 70 (34 mg, 0.10 mmol) were dissolved in DMF(15 mL). The orange solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed.The vessel was heated to and held at 110 ?C for 24 hours, and then the bomb was cooled at arate of 3.7 ?C hr?1. Orange crystals suitable for SCXRD were isolated in 61 % yield. FT-IR(cm?1): 3072 (w), 2861 (w), 1654 (w), 1621 (s), 1542 (m), 1509 (m), 1445 (m), 1384 (s), 1261(w), 1231 (m), 1158 (w) 1122 (m), 1076 (w), 931 (w), 973 (w), 814 (m), 767 (s), 720 (m), 676(m), 612 (m), 603 (w), 507 (w), 457 (m). Elem Calcd for C64H58N4O13S6Zn2: C, 54.35; H,4.13; N, 3.96. Found: C, 54.31; H, 3.72; N, 4.18.392.3. Results and Discussion2.2.3 X-Ray CrystallographyAll crystals were mounted on glass fibers. All measurements were made on a Bruker X8APEX II diffractometer with graphite monochromated Mo-K? radiation. Data were collectedand integrated using the SAINT software package.131 Data were corrected for absorption ef-fects using the multiscan technique (SADABS).132 Structures were solved using direct meth-ods.133 Non-hydrogen atoms were refined anisotropically. All non-N-H hydrogens were placedin calculated positions; all N-H hydrogens were found in the difference map. Refinements for71?82 and 85 were performed using SHELXL-97134 via the WinGX interface.135 Compound79 crystallizes with regions of unresolved electron density in the void volume that could notbe properly modeled. The PLATON/SQUEEZE136 program was used to generate a data setfree of electron density in those regions. Compound 81 crystallizes with significant disorder ofthree of the n-hexyl groups (C55 ? C60, C73 ? C78, and C85 ? C90). Each group was mod-eled in two orientations, and restraints on bond lengths were employed to maintain reasonablegeometries. Additionally, the material crystallizes with at least four molecules of solvent DMFand one water molecule in the asymmetric unit. One of these solvent molecules is disorderedabout a two-fold rotation axis in the unit cell. Finally, there are regions of unresolved electrondensity that could not be properly modeled. As a result, the PLATON/SQUEEZE program wasused to generate a data set free of electron density in those regions. Crystallographic details forcompounds 71?82 and 85 are listed in Table A.1 ? Table A.4. Visualization of the solid statemolecular structures was performed using CrystalMaker?.2.3 Results and Discussion2.3.1 SynthesisThe organic linkers used to synthesize coordination polymers in this chapter are illus-trated in Chart 2.4, and the syntheses of the dicarboxylic acids are described in Scheme 2.1?Scheme 2.3. Oligothiophene dicarboxylic acids 62, 63, 67, 68, and 70 as well as bis(thienyl)benzene acid carboxylic acid 69 were synthesized from Kumada coupling of the appropriatebrominated thiophene precursor, followed by carboxylation of the ?-positions of the terminalthienyl groups.Two main routes for synthesizing coordination polymers were employed and are illus-trated in Scheme 2.4 and Scheme 2.5. Reaction mixtures were either heated in a sealed vessel402.3. Results and DiscussionS S CO 2HHO 2C R R S SHO 2C S CO 2HN N NNSS CO 2HHO 2C RR65, 4,4'-bpy 66, bpe69 626768R =C 6 H 13 HPh 6370R = HPhChart 2.4: Structure of linkers 62?63 and 65?70. S S CO2HHO2C RRS BrR S BrR S SRRMg, I2, THFReflux 1. Pd(dppf)Cl2    THF, reflux2. HCl 1. 2 BuLi, -78 ?C2. 0 ?C, 1 hr3. CO2(s), -78 ?C4. HCl HPhC6H13 626768R =Scheme 2.1: Synthesis of bithiophene dicarboxylic acids 62, 67, and 68.(solvothermal conditions)2 or placed in a vial under atmospheric conditions. To obtain moder-ate yields of coordination polymers, solvothermal reactions were executed with reaction timesof at least 24 hours and at temperatures of at least 110 ?C. Reaction mixtures were cooled at aslow rate of 3.7 ?C hr?1 to promote the growth of single crystals rather than microcrystallinepowders. Dimethylamine (DMA) is found in the solid state molecular structures of 74 and 75.DMA is a known hydrolysis product of DMF137 and has been observed in other coordinationpolymers.138 Reactions to synthesize 74 and 75 are successful when performed at room tem-perature, although DMF replaces DMA in the corresponding axial position, and the reactionoccurs at a much slower rate. Table 2.1 summarizes the preparation methods and structuralaspects of crystallographically characterized coordination polymers.2While the strict definition of solvothermal conditions requires heating a reaction mixture above the boilingpoint of the solvent, this time will be used to describe reactions carried out in sealed Parr bombs.412.3. Results and DiscussionS Br S BrRMg, I2, THFReflux 1. Pd(dppf)Cl2    THF, reflux2. HClRBr S S SRRS S SRR CO2HHO2C 1. 2 BuLi, -78 ?C2. 0 ?C, 1 hr3. CO2(s), -78 ?C4. HClHPh 6370R =Scheme 2.2: Synthesis of terthiophene dicarboxylic acids 63 and 70.S Br Mg, I2, THFReflux 1. Pd(dppf)Cl2    THF, reflux2. HClR SSSS CO2HHO2C 1. 2 BuLi, -78 ?C2. 0 ?C, 1 hr3. CO2(s), -78 ?C4. HClII6 9Scheme 2.3: Synthesis of bis(thienyl)benzene dicarboxylic acid 69.N,N-Diethylformamide (DEF) has been shown to increase pore size and decrease the amountof non-coordinating solvent within coordination polymers.139,140 However, DEF is more diffi-cult to remove than DMF, and pore blocking can occur.139 Reaction of Zn2+ and trans-4,4'-stilbene dicarboxylic acid in DMF forms a dense 2D structure, whereas reaction in DEF formsporous 3D framework.140 Dimethyl sulfoxide (DMSO) was employed as a solvent to determineto what extent in situ decomposition of DMF or DEF is necessary to form coordination poly-mers.137 The 1D coordination polymer 73 was realized, but subsequent reactions with otherlinkers in DEF or DMSO did not produce unique, high yielding, or crystalline products.To increase the electronic and structural diversity of the oligothiophene linkers and sub-422.3. Results and DiscussionZn(NO3)2     6 H2OS SHO2C S CO2HRR Solvothermal conditions76 82S S CO2HHO2C R R SS CO2HHO2CS S CO2HHO2CN N N N717475R  = C6 H13HPh8385R  = HPh7984Scheme 2.4: Synthesis of compounds 71?76, 79, 82, 83, and 85.N N NNS S CO2HHO2C RRZn(NO 3)2      6 H2 O++ 2 weeksDMF, 25?C S S CO2HHO2C RRZn(NO 3)2      6 H2 O++ 2 weeksDMF, 25?C7 77 8R = PhC6H13 8 08 1R = PhC6H13Scheme 2.5: Synthesis of compounds 77,78, 80, and 81.sequent coordination polymers, ?-substituted bithiophenes H23PhT2DC (67) and H23HT2DC(68) were synthesized and incorporated into coordination polymers. Combination of a nitrogen-containing co-linker (4,4'-bpy or bpe) to Zn(NO3)2 ? 6 H2O and H23PhT2DC or H23HT2DCunder solvothermal conditions consistently gives phase-pure 74 or 75 without incorporation of4,4'-bpy or bpe into the structure. However, addition of a nitrogen-containing co-linker withH2T2DC gives a mixture of the desired product with a small amount of 71. In the presence ofa nitrogen-containing ligand under room temperature conditions, compounds 74 and 75 were432.3. Results and DiscussionTable 2.1: Summary of preparation and structure types for crystallographically characterizedcompounds 71?82 and 85.Compound PreparationDimen-sionalityNuclearity, geometryO2C?CO2modea71, 72, 82 Solvothermal 1D Mononuclear, tetrahedral a73 Solvothermal 1D Mononuclear, tetrahedral b74, 75 Solvothermal 2D Binuclear, square pyramidal c76, 78, 79 Solvothermal 3D Binuclear, square pyramidal c77Room temper-ature1DMononuclear, distorted squarepyramidald80Room temper-ature2D Mononuclear, tetrahedral b81Room temper-ature3DMononuclear, tetrahedral; binu-clear, square pyramidalc, e, f85 Solvothermal 1DMononuclear, distorted octahe-dral and square pyramidaldaChart 2.5.occasionally detected in small quantities by PXRD.2.3.2 Solid State Molecular StructuresThe coordination modes of functionalized oligothiophene linkers discussed in this work areshown in Chart 2.5. The solid lines between the O and M atoms indicate a bonding interaction(contact distance < 2.30 ?), while a dashed line suggests a weak interaction between the twoatoms. 2.6 and 2.7 show the simplified coordination environments for compounds 71?77 and79?82. Selected bond lengths and angles for compounds 71?77, 79?82, and 85 are listed inTable A.7?Table A.18.Use of H2T2DC (62) as a linker in solvents DMF, DEF, and DMSO gives isostructuralzig-zag 1-D coordination polymers 71 (synthesized in the Wolf lab prior to the structure be-ing reported124), 72, and 73 as shown in Figure 2.2. The bithiophenes are nearly coplanarwith annular thienyl torsion angles of 166.18(13)?, 168.83(11)?, and 175.11(9)?, respectively.Unsurprisingly, non-coordinating solvent crystallizes in the structures of 71 and 73. Non-coordinating solvent is absent in 72 possibly due to the presence of bulkier ethyl groups onDEF.Solvothermal reactions with ?-substituted bithiophene linkers H23PhT2DC and H23HT2DCgive zinc(II) compounds with extended structures that are dissimilar to 71. Compounds 74 and442.3. Results and DiscussionOOOO MM OOOO MM OOOO MMM OOOO MMM MOOOO MMM M OOOO MMM MOOOO MMM a bf cg heOOOO MM dChart 2.5: Coordination modes for dicarboxylate linkers.75 crystallize in the monoclinic space group P21/n to form 4-connect 2D sheets. Figure 2.3shows the solid state structures of 74 and 75 with Figure 2.3a highlighting the binuclear zincpaddlewheel SBU and Figure 2.3c illustrating the extended structure of both compounds. Fourcarboxylate groups from the organic linker coordinate in a bisbidentate fashion (Chart 2.5c)at the equatorial positions, and DMA caps the axial positions. Zn?O and Zn?N contacts aretypical ranging between 2.02 ? and 2.07 ? (see Table A.10 and Table A.11). The two distinctcrystallographic environments of 3PhT2DC2? are easily distinguishable by their annular S-C-C-S torsion angles. The S2-C5-C6-S1 torsion angle is -110.5(2)? with a phenyl-phenyl centroiddistance of 6.63 ? and the planes of the phenyl rings have an intersection angle of 87.4?.The thiophene rings of S4-C27-C28-S3 have a torsion angle of 56.5(2)? resulting in phenylrings with planes that intersect at 30.5? and have a centroid-centroid distance of 4.22 ?. Thecrystallographic site of 3HT2DC2? has a S1-C5-C6-S2 torsion angle of 68.3(9)?. Within theextended structure, non-coordinated DMF fills the void space between the 2D sheets of 74while n-hexyl chains occupy the space that non-coordinated solvent occupies in 74. No ?-typeinterlayer interaction is present among the phenyl rings.Molecular mechanics modeling of 3,3'-diphenyl-2,2'-bithiophene suggests that an anti con-formation with a thienyl-thienyl torsion angle of 153? is the energetic minimum,128 while theX-ray structure of 3,3'-diphenyl-2,2'-bithiophene and other modeling experiments show themolecule has a S-C-C-S dihedral angle of 69.1? and 69.9?, respectively.141 The calculated en-ergetic minimum conformation of 3,3'-dihexyl-2,2'-bithiophene has an annular torsion angleof 72?.142 These results suggest that the dicarboxylate linkers do not crystallize in a globallyenergy minimized geometry. Other geometric, structure directing effects, interchain or inter-molecular considerations dictate the linker torsion angle and geometry.452.3. Results and DiscussionS S CO2O2C RROOOOOOOOOO OOZnZnDMADMA nOOZnOOX X nOOOO =OOOO = S S CO2O2C SS CO2O2C  Ph C6H13OOOOOO OOZnZnNN nNNZnZn OOOO =OOOO OOOO DMFDMF S S CO2O2C PhPhS S CO2O2C RR  H C6H13=827678747577nDMFDEFDMSOR =R =DMF 717273X =X =Chart 2.6: Simplified coordination environments of compounds 71?78 and 82.462.3. Results and DiscussionZn1 O2 O9O10 O11O12Zn3Zn2O8O7 O6O5O3O4O11O12 Zn3Zn2O9O10O1 Zn1O1O2O3O4N1N2N3N4Zn3Zn2Zn2Zn3 O7O8 O6O5 Zn1N1 N2 Zn3Zn3 Zn2Zn1N NOOOO = N NS S CO2O2C C6H13C6H13OOOOOO OOZnZnNN nS S CO2O2COOOO S S CO2O2C PhPhZn OOOO NN nOOOO =807985== S SO2C S CO2PhPhOO =OOOOOO Zn1DMFDMFZn2DMFDMFH2O n OOOO81Chart 2.7: Simplified coordination environments of compounds 79?81 and 85.472.3. Results and Discussiona)b)c)Figure 2.2: Solid state molecular structures of a) 71, b) 72, and c) 73. Hydrogens, disorder, andnon-coordinating solvent have been omitted for clarity. Thermal ellipsoids are shown at 50 %probability.482.3. Results and Discussiona)b) c)Figure 2.3: Solid state molecular structures of a) 74 and b) 75. Hydrogens and non-coordinating solvent have been omitted for clarity. Ellipsoids are shown at 50 % probability.c) Simplified extended structure of 74 and 75.Addition of ditopic ligands such as linear 4,4'-bipyridine (4,4'-bpy, 65) or photoactive trans-1,2-bis(4-pyridyl)ethylene (bpe, 66) can offer structural variation by linking 1D and 2D coordi-nation polymers to form materials of higher dimensionality. This method was employed in anattempt to synthesize structurally robust 3D coordination polymers. Linker bpe was exploredbecause of its ability to undergo in situ isomerization or post-synthetic [2+2] photocycliza-492.3. Results and Discussiontion.60 None of the materials incorporating bpe showed the correct geometric requirements forphotocyclization, but the incorporation of bpe resulted in compounds with different topologyand properties than the 4,4'-bpy analogs.Compounds 76 and 79 are two and three-fold, respectively, interpenetrated 3D frameworkcomprised of zinc(II) binuclear paddlewheel clusters with T2DC2? molecules at the basal po-sitions (similar to 74 and 75) and N-heterocyclic ligands 4,4'-bpy and bpe, respectively, at theaxial positions (Figure A.1). The simplified framework has a pcu topology where the zincbinuclear paddlewheel acts as a six-connected node. There is one crystallographic T2DC2?environment that adopts a bis-bidentate coordination mode (Chart 2.5c). The annular torsionangle is for 76 is 173.5(6)? and 145.6(4)? for 79. The pyridyl rings are coplanar in 79 andtwisted and disordered in 76. A preliminary3 X-ray structure of 78 was obtained, and thecoordination polymer is isostructural to 76 and 79.Upon reaction of the zinc precursor, H23PhT2DC, and 4,4'-bpy, a coordination networkforms instead of insertion of 4,4'-bpy into the axial positions of the binuclear zinc paddlewheel.Figure 2.4 shows that compound 77 is a 3-connected uninodal coordination network with aladder-type structure. The mononuclear Zn2+ node has a distorted square pyramidal coordi-nation environment where the pyridyl nitrogen resides at the axial position and carboxylatesand DMF occupy the basal positions. One non-coordinating DMF and one non-coordinatingH2O per unit cell reside between the ladder-like chains. ?2?Carboxylate-metal distances are2.0204(17) ? (O1?Zn1) and 2.29774(18) ? (O2?Zn1), while the ?1?carboxylate-metal dis-tances are 1.9560(16) ? and 2.847(2) ?. Disorder is present at the coordinating DMF. The4,4'-bpy rings are coplanar with a C24-C25-C25-C26 torsion angle of -1.13(4)?, while thethienyl rings are perpendicular to each other with a S-C-C-S torsion angle of -89.9(3)?. Phenylrings are well spaced at a distance of 5.67 ?, and the planes of the phenyl rings intersect at33.2?.Colorless crystals of compound 80 form after the parent reaction mixture sits at room tem-perature for a few days. The zinc center has a tetrahedral geometry and is coordinated to twobis-monodentate 3PhT2DC2? and two bpe ligands (Figure 2.5a). Each carboxylate adopts a(?1 ? ?1)??2 coordination (Chart 2.5b). Rather than replacing DMA in the structure of 74 andacting as a linker to connect 2D sheets of 3PhT2DC2? groups, bpe is part of a 2D grid. Zn?Ocontact lengths of 1.969(3) ? (Zn1?O1), 1.962(4) ? (Zn1?O3) and approximately 2.69 ? and2.86 ? clearly indicate one oxygen atom per carboxylate is involved in bonding. The S1-C5-C6-S2 torsion angle of the bithienyl unit is -60.0(5)?, the planes of the phenyl rings intersectingat 41.2?, and the phenyl-centroid contact distance is 4.62 ?. This distance is longer than that3R-factor > 10 %, which is attributed to multiple twin components and severe disorder of the n-hexyl chains.502.3. Results and Discussiona)b)Figure 2.4: a) Solid state molecular structure and b) the extended structure of 77. Hydrogensand non-coordinating solvent have been omitted for clarity. Ellipsoids are shown at 50 %probability.observed for 74. The zinc-linked bpe chains shown in Figure 2.5b have a Zn-Zn-Zn angleof 131.3?, whereas zinc(II) atoms along the chain of 67 are colinear. Zn-Zn-Zn angles at thebpe-67 intersection are 87.5? and 92.5?, nearly right angles.The room temperature reaction to synthesize compound 81 affords yellow crystals after oneweek. Compound 81 is a two-fold interpenetrated three-dimensional framework belonging tothe space group C2/c. The framework has a (4,6)-connected seh topology and is assignedthe Schla?fli symbol of (3.42.52.6)(32.42.52.64.74.8). Notably, interpenetration still occurs withn-hexyl groups in the framework. The bpe linker appears to act as a spacer and open up the512.3. Results and Discussiona)b)131?Figure 2.5: a) Solid state molecular structure of 80. Hydrogens and non-coordinating solventhave been omitted for clarity. Ellipsoids are shown at 50 % probability. b) Simplified extendedstructure of 80; red: bpe, blue: 68, green: metal center.coordination polymer such that there is room for interpenetration.Figure 2.6a shows the coordination environment within compound 81. There are two dis-tinct zinc environments: a binuclear paddlewheel SBU and a mononuclear four-coordinatecenter. The binuclear paddlewheel cluster is coordinated to four carboxylate groups from twocrystallographically independent 3HT2DC2? and two pyridyl moieties from two crystallograph-ically independent bpe in the axial positions. The mononuclear four-coordinate center coordi-nates to two 3HT2DC2? and two bpe ligands. In total, there are three unique 3HT2DC2? envi-522.3. Results and Discussiona)b)c) d)Figure 2.6: a) Solid state molecular structure of 81. Hydrogens, n-hexyl chains, and non-coordinating solvent have been omitted for clarity. Ellipsoids are shown at 50 % probability.b) The ribbon feature of 81. c) The simplified structure of 81. Dashed lines in red and greenillustrate the ribbon feature, and the solid blue line represents the linking 3HT2DC2? groups.d) The extended structure of 81.532.3. Results and Discussionronments with annular torsion angles of 68 are -118.4(3)? (S1-C5-C6-S2), 65.4(3)? (S3-C15-C16-S4), and 117.6(4)? (S5-C25-C26-S6). The corresponding coordination modes to theselinkers are illustrated in Chart 2.5e, f, and c, respectively. The pyridyl rings are nearly coplanarfor one bpe group (-178.5(3)?, C47-C48-C49-C50), but the other bpe ligand has pyridyl ringsthat are twisted by approximately 20? (-168.7(4)?, C35-C36-C37-C38). Ribbons consisting oftwo 68 ligands, two bpe ligands, and two binuclear centers joined by two mononuclear centers(Figure 2.6b) span the extended structure.Looking down the c-axis, there are two planes oriented 50? from each other that the ribbonsoccupy (Figure 2.6c, red and green lines) which intersect and share nodes at the mononuclearzinc center. In addition, the ribbons of the two planes are connected via a 3HT2DC2? linkage(linker belonging to S5 and S6) of two binuclear SBUs (Figure 2.6c, blue line). Figure 2.6dshows that disordered n-hexyl chains of 3HT2DC2? fill much of the free space of the coordina-tion polymer. This type of self-assembled aggregation has been previously observed.141,143It ispossible that the occupancy of the otherwise void space by the n-hexyl chains plays a key rolein the formation of this unusual solid state structure.Numerous attempts were made to grow single crystals of zinc(II) triaryl compounds in-cluding terthienyl, dithienothiophene, and bis(thienyl)benzene coordination polymers. Singlecrystals suitable for SCXRD were achieved for two compounds, one with a bis(thienyl)benzenelinker ([Zn0.5(TPhTDC)0.5(DMF) ? DMF]n, 82) and one containing a phenyl-functionalizedterthienyl linker ([Zn2(Ph2T3DC)2DMF4H2O]n, 85). Both 82 and 85 are 1D coordinationnetworks. Compound 82 is similar in structure to 71-73 with tetrahedral Zn2+ centers (Fig-ure A.2). Disordered non-coordinating DMF is sandwiched between chains of compound 82 ata phenyl centroid-DMF distance of 3.55 ?. The thienyl-phenyl torsion angle of S1-C5-C6-C8is 32.88(18)?.Figure 2.7 shows the solid state molecular structure of compound 85. The two zinc(II)coordination environments within compound 85 are square pyramidal (Zn1) and distorted oc-tahedral (Zn2). Three carboxylate oxygens and one DMF occupy the equatorial positions,and DMF and water (for Zn2) occupy the axial positions. The planes of the two Ph2T3DC2?groups are positioned in a near-orthogonal orientation. Notably, the annular torsion angles ofthe trans, trans thiophene rings are relatively planar for a compound with peripheral phenylgroups with values of 175.4(6)? (S1-C4-C5-S2), 161.5(5)? (S2-C9-C10-S3), -174.2(5)? (S4-C31-C32-S5), and -150.7(6)?(S5-C35-C36-S6).542.3. Results and DiscussionFigure 2.7: Solid state molecular structure of 85. Non O?H hydrogens have been omitted forclarity. Ellipsoids are shown at 50 % probability.2.3.3 PXRDThe phase purity of the coordination polymers was determined using powder X-ray diffrac-tion (PXRD). When available, the patterns predicted from the single crystal X-ray diffractiondata (SCXRD) were compared to the experimental patterns. On a whole, the PXRD patternsof the bulk material matches the pattern calculated from the SCXRD data. There is a broadpeak present in 81 that is not predicted in the simulated pattern and grows in with exposure toatmosphere. This feature is assigned to the loss of non-coordinating solvent144 and collapse ofthe framework upon desolvation. The experimental and predicted PXRD patterns of 82 do notmatch as well as expected (Figure B.12). The difference in the patterns could be explained bya collapse of the structure upon removal from solvent, preferred orientation of the powder thatcauses some orientations to dominate, or that the crystal evaluated is a minor product of thesynthesis and does not reflect the bulk material.Using the presented crystallographic information along with the structural informationgained from manganese terthienyl coordination polymers (Chapter 3) and careful inspection ofPXRD patterns, some structural information was obtained from PXRD patterns. Too few well-defined, unique reflections are present in the PXRD pattern of 83 (Figure B.13) to determinethe unit cell parameters. The PXRD pattern of 84 (Figure 2.8) contains enough well-definedpeaks to determine the space group and unit cell using autoindexing tools within TOPAS.145Several unit cell parameters with figures of merit exceeding values of 20 were found to bethe best solutions. All unit cell parameters had similar values and belonged to the monoclinicspace group P21. The best fit unit cell has dimensions of a = 12.03 ?, b = 31.37 ?, c = 8.35 ?,and ? = 114.7?, and this cell is compared to the experimental powder pattern in Table 2.2.The presence of 4,4'-bpy in the coordination polymer was confirmed by elemental analysis552.3. Results and Discussion10 20 30 40 5005001000150020002? (?)Intensity(Countss?1 )Figure 2.8: PXRD pattern of 84.Table 2.2: Miller indices of compound 84 and values of 2? (theoretical and experimental).hkl Theor. Expt. hkl Theor. Expt.0 2 0 5.63 5.63 1 5 0 16.29 16.261 0 0 8.09 - - - 2 -2 -1 16.53 16.511 1 0 8.57 8.55 0 6 0 , 1 1 1 16.95, 17.01 16.991 2 0 9.86 9.83 2 2 0 17.18 17.160 4 0 11.28 11.26 2 -3 -1, 1 2 1 17.70, 17.71 17.691 -1 -1 11.43 11.41 1 -5 -1 17.98 17.970 0 1, 1 3 0 11.67, 11.71 11.67 2 3 0 18.32 18.290 1 1 12.01 - - - 1 6 0, 1 3 1 18.81, 18.82 18.790 2 1 12.96 12.94 2 -4 -1 19.23 19.221 4 0, 1 -3 -1 13.90, 13.95 13.93 1 6 -1 20.30 20.280 3 1 14.42 14.39 -2 0 2 22.25 22.20-2 0 1 15.53 15.50 2 -2 -2 22.97 22.941 4 -1 15.83 15.82 2 0 1 23.71 23.69corresponding to 1:1 T3DC2?:4,4'-bpy. Two T3DC2? linkers per unit cell appear to lie alongthe b-axis, while 4,4'-bpy is likely along the a-axis. The a-axis dimension is longer than celldimensions for compounds where 4,4'-bpy is along an axis. For example, in [M2+TDC(4,4'-bpy)]n (56), the b-axis ranges between 11.4 ? and 11.6 ?. A polynuclear metal center couldaccount for the slightly larger dimension as in the case of 76 where 4,4'-bpy resides along thec-axis with a unit cell parameter of 13.86 ?. Attempts at Rietveld refinement of atom positions562.3. Results and Discussionwere unsuccessful.2.3.4 Thermal StabilityThermogravimetric analysis (TGA) was performed to analyze the composition and evaluatethe thermal stability of selected coordination polymers. Table 2.3 summarizes the results of theanalyses. Loss of both coordinating and non-coordinating solvent is observed. Major decom-position occurs at ?350 ?C and is attributed to the loss of the organic linkers. In general, higherthermal stability correlates to a framework of higher dimensionality. For the bithienyl com-pounds, the remaining weigh corresponds to the formation of ZnO along with a small amountof unidentifiable decomposition products. A large discrepancy exists between the theoreticaland calculated values for 83. Either incomplete decomposition occurred, the metal node is apolynuclear cluster, or significant impurities are present in the compound. The decompositiontemperature of 84 would suggest that the material is not composed of 1D chains and has ahigher order dimensionality.Table 2.3: Thermogravimetric data for selected compounds.CompoundTemperature of initialweight loss (?C)Final weight (%)(experimental)Final weight (%)(calculated)a71 120, 185, 300 16.2 15.374 220, 340 13.6 13.075 130, 315, 525 15.1 15.376 220, 350 18.5 20.679 130, 320 16.2 20.080 300, 370 9.4 10.181 240, 400 10.7 11.583 380 24.7 16.3b84 130, 360 13.8 12.6ba Based on ZnO being the identity of the decomposition product.b Presumed composition from elemental analysis.2.3.5 Electronic Absorption and Emission SpectraTo investigate the excited state electronic behavior of these coordination polymers, thephotoluminescence spectra of both the ligands and coordination polymers were obtained andare summarized in Table 2.4. The photoluminescence spectra of oligothiophene ligands in the572.3. Results and DiscussionTable 2.4: Solid state photoluminescence data for linkers and coordination polymers 71?85.Compound Absorption/Excitation Emission(?max, nm) (?max, nm)bpy (65) 300, 350 360, 470bpe (66) 295a, 430 400, 52562 395 49063 515 60567 390 47068 385 430,b 49069 360-460 52570 340, 430 545, 59071?73 370, 410 450, 48574 380 47075 395 43576 410 50577 395 49078 405 47079 380 50080 380 47081 390, 450 435, 460, 53082 300, 380 48083 400?500 67584 350, 470 480, 505, 540, 58585 350?450 480, 525, 570aSolution state absorption. bSolution state emission.solid state have single features and broad emission bands. In solution, the emission maxima areidentical to those observed in the solid state with the exception of 68 which exhibits a blueshiftto ?max = 430 nm. In general, the emission features of the fluorescent coordination polymersare attributed to the photoluminescent behavior of the constituent ligands. These species allhave short excited state emission lifetimes consistent with singlet emission from ?-?* states.The emission ?max of the coordination polymers matches the emission of the constituent thienyllinkers with the exception of 75 and 83. Linker-based (3HT2DC2?) emission of 75 blue shiftsfrom ?max = 485 nm to 430 nm upon coordination to zinc, whereas ligand-based (T3DC2?)emission undergoes a significant red shift in 83 from ?max = 600 nm to 680 nm when coor-dinated to zinc(II). The emission of compound 75 closely matches the profile of proligand 68in solution, and the geometry of the coordination polymer may reflect its solution state ori-582.3. Results and Discussionentation. Planarization or rigidification140 of the 63 unit within the coordination polymer oraggregation induced effects146 are possible explanations for the bathochromic shift in emissionfor 83.The emission of compounds 67, 74, and 77 are quite intense, possibly due to the phenylrings preventing close contact between the bithienyl units and acting as ?molecular bumpers.?147The head-to-head nature of compounds bearing n-hexyl chains would also prevent strong in-termolecular interactions of the thienyl units for both the linker and subsequent coordinationcompounds. As a consequence of utilizing functionalization of the 3-positions, steric effectswill hinder the planarization of the thienyl linkers.With the exception of 80 and 81, the emission intensities are comparable to the emissionintensities of their respective bithienyl ligands in the solid state. Fluorescence efficiencies forpoly(thiophene)s in solution are significantly higher than in the solid state.147 Non-radiativemechanisms in the solid state that are present in poly(thiophene)s include excimer formationvia interchain interaction and conformational and linkage defects.110 However, the emissionintensities for 80 and 81 are significantly weaker than for 74 and 75 or those that contain4,4'-bpy (77 and 78). Additionally, this reduction in emission intensity is not observed whencomparing 71 to 79, which contains a bpe linker.One potential explanation for these results is that the bpe linker is transferring or quenchingthe emission originating from 67 and 68 within 80 and 81, respectively. Other coordinationpolymers containing bpe do not exhibit fluorescence quenching.148?153 The observation thatemission intensity is not reduced in 79 suggests that bpe on its own is not quenching bithienyl-based emission. To probe if bpe is responsible for the reduced emission intensity attributed tothe bithienyl linkers, the photoluminescence of the constituent linkers of compound 81 (68 andbpe) were studied in greater detail.The emission profiles of mixtures of bpe and 68 were investigated in the solution (Fig-ure 2.9) and in the solid state (Figure 2.10). In solution, addition of bpe beyond the ratio foundin 81 caused only a minor increase in emission intensity. This can be attributed to the ab-sorption maximum of bpe occurring at 295 nm in solution and, as a consequence, a minimaloverlap between 68-based emission and bpe absorption. In the solid state, bpe has a broadabsorption range of 390 nm?480 nm with ?max at 430 nm, and some overlap between the bpeabsorption spectrum and with the emission profile of 68 (?max = 490 nm) occurs. In spite of thisoverlap, 68-based features (blue trace) dominate the emission spectrum of the solid mixture ofthe proligands, while excitation at the energy bpe absorbs generates weak emission (red trace)(Figure 2.10).592.3. Results and Discussion300 350 400 450 500 55005000100001500020000250000x bpe1x bpe2x bpe5x bpeWavelength (nm)Emission(Countss?1 )Figure 2.9: Fluorescence excitation (dashed) and emission (solid) spectra of 68 (1.25 ? 10?5M) and bpe in MeOH, ?ex = 330 nm, ?em = 425 nm.300 350 400 450 500 550 600020000400006000080000100000      ?em = 490 nm?ex = 385 nm?em = 540 nm?ex = 460 nmWavelength (nm)Emission(Countss?1 )Figure 2.10: Fluorescence excitation (dashed) and emission (solid) spectra of 3:2 68 and bpein the solid state.602.3. Results and Discussion300 350 400 450 500 550 600020000400006000080000100000 ?em = 430 nm?ex = 400 nm?em = 540 nm?ex = 460 nmWavelength (nm)Emission(Countss?1 )Figure 2.11: Fluorescence excitation (dashed) and emission (solid) spectra of 81.These studies suggest if incomplete energy transfer is the quenching mechanism for 68-based emission within compound 81, the linkers need to be within a structured frameworkto achieve the appropriate proximity and electronics required for resonance energy transfer.58Additionally, the 68 component of the emission spectrum needs to overlap well with the ab-sorption of bpe. The spectral overlap between the two constituent linkers is modest, whilethe blue-shifting of 68-based emission within coordination polymers causes very good overlapbetween bpe-based absorption and 68-based emission.Features of both organic linkers are readily discernible in the emission spectrum of 81(Figure 2.11), and Figure 2.12 illustrates the proposed energy pathways within 81. Excitationof 81 at 400 nm (black stars) directly excites the 3HT2DC2? component of the coordinationpolymer. Due to the broad range of the bpe absorption, this linker is also directly excited.However, the studies of the constituent linkers (see Figure 2.9 and Figure 2.10) show the 68-based emission dominates in intensity compared to bpe. As a result, emission based from 68at 430?460 nm (blue star) with minor contributions from bpe centered at 540 nm (red star) areexpected (Figure 2.11, blue trace). Excitation of 81 at 460 nm (brown star) causes bpe-basedluminescence at 540 nm (Figure 2.11, red trace).Inspection of Figure 2.11 shows the emission intensity at 430 nm (blue trace) is less than612.4. Conclusionsthe intensity at the excitation wavelength of 400 nm (black trace). This suggests some of thelight emitted from 3HT2DC2? within 81 is being reabsorbed by bpe or the excited 3HT2DC2?participates in a through-space resonance energy transfer to the bpe moiety (green star).57,58These processes would account for both the larger bpe character in the emission spectrum of81 as well as the overall decrease in emission intensity of 81 compared to compounds 75, 78,and 79. Non-radiative decay processes (purple star) such as intersystem crossing and decayto low lying triplet states are known to quench singlet emission and may occur within 81.154Overall, the structured environment of linkers 68 and bpe within 81 induces photophysicalphenomenon that differ from the constituent linkers.O OO OO O O OZnZnN NN S S OO Zn NO N NC6H13 C6H13!ex = 400 nm!em = 430?465 nmNon-radiative decay pathwayEnergy transfer (incomplete)!em = 540 nm!ex = 400 nm!ex = 460 nmFigure 2.12: Proposed energy transfer scheme for 81.2.4 ConclusionsPhotoluminescent oligothiophene dicarboxylic acids and coordination polymers have beensynthesized and characterized. The structures of these materials can be tuned by changing thefunctionality at the ?-position of the thienyl unit. The annular torsion angles of 3PhT2DC2? (67622.4. Conclusionsand 3HT2DC2? (68) in coordination polymers deviates from the calculated energy-minimizedgeometry of 3,3'-diphenyl-2,2'-bithiophene and 3,3'-dihexyl-2,2'-bithiophene. Additionally,the near co-facial interaction of the phenyl moieties in compounds 74, 77, and 80 is not closeenough to suggest significant ?-? interaction occurs between the groups. Addition of aliphaticfunctional groups drive out non-coordinating solvent as seen in 75. In the 3D coordinationpolymer 81, the presence of n-hexyl chains can lead to the formation of hydrophobic pock-ets. Addition of an N-heterocyclic ligand results does not guarantee the formation of a 3Dmaterial: coordination networks and 2D sheets as well as 3D frameworks with varied topol-ogy were synthesized. Indexing of the PXRD pattern of 84 was successful, and the unit celldimensions show elements of both 4,4'-bpy and T3DC2?. Most compounds retained similaremission properties to their constituent ligands, while 75 and 83 underwent noticeable blueand red-shifts, respectively. The emission intensity of 81 was drastically reduced via contribu-tions of incomplete energy transfer between the linkers in a structured coordination polymer.This behavior could be beneficial for emission-based applications of these materials such as inchemical sensors or light-emitting devices.63Chapter 3Non-Luminescent Coordination Polymers3.1 IntroductionThe synthesis and characterization of coordination polymers containing metal centers with-out d10 closed shell valency is of particular interest due to the local155 and global156?160 struc-tural diversity, potential mixed valence character,161,162 electronic activity,163 and magneticproperties.164?166 Although the previous chapter addressed the relation between the physicaland electronic structure of oligothiophene coordination polymers, the solid state molecularstructures of non-luminescent materials and their magnetic behavior are of interest. The struc-tural data obtained from these compounds provides valuable information for engineering spe-cific solid state interactions within luminescent coordination polymers.Magnetic properties are intimately related to a materials metal-linker coordination and ex-tended structure.75 Spin-canting magnetism is the alignment of magnetic spins in antiferro-magnetic materials that produces a net magnetic moment and can occur in compounds thatlack inversion symmetry. Temperature-dependent structural phase changes will often inducesuch changes in magnetic character. Defects in the crystal structure of antiferromagnetic ma-terials can also cause weak net magnetic moments.Weak ferromagnetic ordering occurs in the acentric 3D coordination polymer [Mn(4,4'-bpy)(N3)2]n (86, Chart 3.1), in which the Mn2+ center coordinates with 4,4'-bpy in the axialpositions and azide groups in the equatorial positions.167 An antiferromagnetic to weak fer-romagnetic transition is observed at TC = 42.5 K and is assigned to a change in Mn?N3?Mn interaction rather than Mn-4,4'-bpy-Mn interaction. A similar transition occurs in the 3Dcoordination polymer [Mn2(bpt)(pa)2(N3)]n (bpt = 3,5-bis(2-pyridyl)-4H-1,2,4-triazolate, pa= picolinate) (87) via changes in the intradimeric Mn?N3?Mn and Mn?bpt?Mn bridges atTC = 6.5 K.168As eluded to in Chapter 2, peripheral functional groups on organic linkers influence theextended structure of coordination polymers. Those containing linkers with alkyl chains havebeen reported,143,169?171 but generally little emphasis is given to the exact influence of aliphaticfunctional groups on the extended structure of coordination polymers. Coordination polymers643.1. Introduction NNN NNNNMn N3N3 N3N3 NN Mn N3 MnOO N O OO ON NOO N8 6 8 7Chart 3.1: Metal center coordination sphere of compounds 86 and 87.167,168with picolyl-triazole linkers containing n-butyl, n-pentyl, and n-hexyl groups form 1D struc-tures upon coordination to Zn2+.143 The materials have similar 4-coordinate Zn2+ environments.Depending on the length of the alkyl group at the 4-position of the triazole, the 1D extendedstructure is zig-zag, helical or wave-likeFew examples of crystallographically characterized metal-organic frameworks with conju-gation pathways extending over at least three aryl groups have been reported. Those containingp-terphenyl linkers 1,1':4',1''-terphenyl-3,3''-dicarboxylate (88) and 1,1':4',1''-terphenyl-4,4''-dicarboxylate (89) have been limited to Zn2+ species.172,173 Zheng and co-workers recentlyreported a series of mixed linker coordination polymers incorporating the tetraaryl linker 5,5'-bis(4-pyridyl)-2,2'-bithiophene (90).174 Most of the coordination polymers discussed are 3Dframeworks, and all of the structures are highly penetrated owing to the large void volumethe linker provides. Terthiophene coordination polymers have been synthesized from chemi-cal or electrochemical methods but have not produced materials that have been characterizedcrystallographically.108,126,175This chapter expands the library of oligothiophene coordination polymers using linkersthat were introduced in Chapter 2. Attention is given to how phenyl and n-hexyl substituentsas well as thiophene oligomer length influence the extended structure. In addition, the magneticbehavior of selected coordination polymers and the correlation between magnetic susceptibilityand structure is discussed.653.2. ExperimentalO 2 C CO 2 O 2 C CO 2 S S NN2- 2-8 8 8 9 9 0Chart 3.2: Triaryl and tetraaryl linkers 88?90.172?1743.2 Experimental3.2.1 GeneralMnCl2 ? 4 H2O, Cu(NO3)2 ? 2.5 H2O, CoCl2 ? 6 H2O, and n-butyllithium were purchasedfrom Sigma-Aldrich. N,N-Dimethylformamide (DMF) was purchased from Fisher Scientific.Dithieno[3,2-b:2',3'-d]thiophene-2,6-dicarboxylic acid (H2DTTDC, 91) was prepared by liter-ature procedure.176 The preparation of compounds 63, 67, 68, and 70 are described in Section2.2.THF was distilled from Na/benzophenone. EI mass spectra were obtained using a KratosMS-50 mass spectrometer coupled to a MASPEC data system. CHN elemental analyses wereperformed using a EA1108 elemental analyzer. Infrared spectra were obtained on a ThermoNicolet 6700 with a Smart Orbit accessory in the range of 4000-400 cm?1. Thermogravimet-ric analyses (TGA) were performed using a Perkin Elmer Pyris 6 Thermogravimentric Ana-lyzer under a nitrogen atmosphere at a rate of 10? min?1. Magnetization measurements wereperformed using a Quantum Design MPMS-XL-7S SQUID magnetometer with an Evercool-equipped liquid helium dewar. Diamagnetic contributions to the magnetic susceptibility werecorrected for using Pascal?s constants.177 Powder X-Ray diffraction (PXRD) patterns were ob-tained on a Bruker D8 Advance instrument with graphite monochromated Cu-K? radiation ata scan rate of 5? min?1. TOPOS49 was used to determine net topology. TOPAS145 was used toindex PXRD patterns.3.2.2 Procedures[Mn(3PhT2DC)(DMF)0.45(H2O)2.55 ? 1.55 DMF]n (92):MnCl2 ? 4 H2O (0.020 g, 0.10 mmol) and 67 (0.041 g, 0.10 mmol) were dissolved in DMF(5 mL). The solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed. The ves-663.2. Experimentalsel was heated to and held at 110 ?C for 48 hours, and then the bomb was cooled at a rateof 3.7 ?C hr?1. Colorless crystals of [Mn(3PhT2DC)(DMF)0.45(H2O)2.55 ? 1.55 DMF]n wereisolated in 73 % yield. FT-IR (cm?1): 3430 (w, br), 2933 (w, br), 1637 (s), 1570 (s), 1528 (m),1494 (m), 1410 (s), 1372 (s), 1347 (s), 1209 (m), 1109 (m), 1062 (w), 869 (w), 846 (w), 765(m), 698 (m), 628 (w), 550 (w), 497 (w). Elem Calcd for C28H26N2O8.54S2Mn: C, 52.09; H,4.06; N, 4.34; Found C, 52.03; H, 4.61; N, 4.71.[Cu(3PhT2DC)(EtOH) ? 2 DMF]n (93):DMF (2 mL) was layered on top of a DMF solution (2 mL) of Cu(NO3)2 ? 2.5 H2O (0.012 g,0.050 mmol). A 1:1 EtOH/DMF (2 mL) solution of 67 (0.020 g, 0.050 mmol) was layered uponthe buffering DMF layer. Blue-green crystals of [Cu(3PhT2DC)(EtOH) ? 2 DMF]n suitable forSCXRD were allowed to grown for three weeks and were isolated in 37 % yield. FT-IR (cm?1):3055 (m, br), 1532 (s), 1496 (m), 1417 (s), 1375 (m), 1348 (m), 1215 (m), 1126 (w), 1070 (w),873 (m), 804 (w), 756 (s), 717 (w), 693 (m), 632 (w), 598 (w), 491 (w). Elem Calcd forC30H31N2O7S2Cu: C, 54.57; H, 4.89; N, 4.24. Found C, 55.19; H, 4.02; N, 3.66.[Mn6(3HT2DC)6(DMF)3(H2O)5 ? x DMF ? y H2O]n (94):MnCl2 ? 4 H2O (0.020 g, 0.10 mmol) and 68 (0.042 g, 0.10 mmol) were dissolved in DMF(5 mL). The solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed. The ves-sel was heated to and held at 110 ?C for 48 hours, and then the bomb was cooled at a rateof 3.7 ?C hr?1. Colorless crystals of [Mn6(3HT2DC)6(DMF)3(H2O)5 ? x DMF ? y H2O]n wereisolated in 56 % yield. FT-IR (cm?1): 2925 (m), 2854 (m), 1647 (m), 1565 (m), 1530 (m), 1421(s), 1386 (s), 1353 (s), 1258 (w), 1195 (w), 1102 (m), 1016 (w), 871 (w), 774 (s), 714 (m), 677(m), 484 (w). Elem Calcd for C141H199N3O32S12Mn6: C, 53.55; H, 6.34; N, 1.33; Found C,54.40; H, 6.19; N, 2.44.4[Co(DTTDC)(C5H5N)(MeOH)(H2O)0.5 ? 2 MeOH]n (95):A solution of CoCl2 ? 6 H2O (0.018 g, 0.075 mmol) in MeOH (5 mL) was layered upon asolution of 91 (0.021 g, 0.075 mmol) in pyridine (5 mL). Red crystals of Co(DTTDC)(C5H5N)-(MeOH)(H2O)0.5 ? 2 MeOH]n suitable for SCXRD were allowed to grow for four weeks and4The discrepancy between the calculated and experiment elemental analysis is associated with the presence ofnon-coordinated solvent that was removed during the SQUEEZE protocol.673.2. Experimentalwere isolated in 19 % yield. FT-IR (cm?1): 3100 (m, br), 1601 (w), 1538 (m), 1496 (s), 1485(m), 1442 (m), 1371 (s), 1326 (m), 1217 (w), 1167 (m), 1075 (w), 1040 (w), 857 (w), 765 (m),748 (m), 692 (m), 628 (w), 581 (m), 462 (w). Elem Calcd for C17.5H18NO7S3Co: C, 41.26; H,3.56; N, 2.75. Found C, 40.52; H, 4.21; N, 2.38.[Mn(T3DC)(H2O)2]n (96):MnCl2 ? 4 H2O (0.020 g, 0.10 mmol) and 63 (0.034 g, 0.10 mmol) were dissolved in DMF(5 mL). The solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed. The ves-sel was heated to and held at 110 ?C for 48 hours, and then the bomb was cooled at a rateof 3.7 ?C hr?1. Yellow-orange crystals of [Mn(T3DC)(H2O)2]n were isolated in 81 % yield.FT-IR (cm?1): 3212 (m, br), 1547 (m), 1507 (s), 1439 (s), 1380 (s), 1111 (m), 1064 (w), 1034(m). 858 (m), 785 (m), 769 (s), 699 (w), 676 (w), 631 (w), 534 (w), 476 (m). Elem Calcd forC14H10O6S3Mn: C, 39.53; H, 2.37; Found C, 39.63; H, 2.49.[Mn(T3DC)(H2O)1.5]n (97):Red-orange crystals of 97 were grown from the solvothermal reaction mixture of 96 andisolated in less than 1 % yield. FT-IR (cm?1): 3590 (w), 1641 (sh), 1626 (m), 1557 (s), 1530(m), 1509 (m), 1446 (m), 1435 (m) 1361 (vs), 1128 (m), 1066 (m), 1031 (m), 866 (m), 767 (s),680 (w), 642 (w), 541 (w), 483 (m). Elem Calcd for C14H9O5.5S3Mn: C, 40.39; H, 2.18; FoundC, 39.54; H, 2.07.[Mn(Ph2T3DC)(DMF)2]n (98):MnCl2 ? 4 H2O (0.020 g, 0.10 mmol) and 70 (0.049 g, 0.10 mmol) were dissolved in DMF(5 mL). The solution was transferred to a 23 mL Teflon-lined Parr bomb and sealed. Thevessel was heated to and held at 110 ?C for 48 hours, and then the bomb was cooled at a rateof 3.7 ?C hr?1. Dark yellow crystals of [Mn(Ph2T3DC)(DMF)2]n were isolated in 64 % yield.FT-IR (cm?1): 3089 (w), 2936 (w), 1639 (s), 1563 (s), 1528 (m), 1441 (m), 1379 (s), 1252 (m),1213 (w), 1105 (m), 1069 (w), 1024 (w), 904 (w), 814 (m), 770 (s), 701 (m), 671 (m), 628(w), 613 (w), 510 (w), 465 (m). Elem Calcd for C32H28N2O6S3Mn: C, 55.89; H, 4.10; N, 4.07;Found C, 54.91; H, 4.09; N, 3.93.683.3. Results and Discussion3.2.3 X-Ray CrystallographyAll crystals were mounted on glass fibers. Diffraction from 92 and 96 was measured on aBruker APEX DUO diffractometer with graphite monochromated Cu-K? radiation. Diffrac-tion from 93?95 and 97 was measured on a Bruker APEX DUO diffractometer with graphitemonochromated Mo-K? radiation. Diffraction from 98 was measured on a Bruker X8 APEX IIdiffractometer with graphite monochromated Mo-K? radiation. Data were collected and inte-grated using the SAINT software package.131 Data were corrected for absorption effects usingthe multiscan technique (SADABS).132 Structures were solved using direct methods.133 Non-hydrogen atoms were refined anisotropically except for atoms C37?C38, C43?C44, C59?C60,C84?C88, C107?C110, C130?C132, C137, C148?C150, N7, and O34 of 94. All non-O-Hhydrogens were placed in calculated positions; O-H hydrogens in 95 and 97 were found onthe difference map while O-H hydrogens in 92, 94, and 96 were not modeled. Refinementsfor 92-98 were performed using SHELXL-97134 via the WinGX135 interface. Compound 92crystallizes with disordered coordinating and non-coordinating solvent at the O8 site, and thegroup was modeled in two orientations. Compound 93 is a three-component twin. Compound94 crystallizes with significant disorder in one n-hexyl group (C17-C22), and the group wasmodeled in two orientations. Restraints on bond lengths for n-hexyl groups were employed tomaintain reasonable geometries. Compound 95 crystallizes with one solvent molecule disor-dered about a two-fold rotation axis in the unit cell. There are regions of unresolved electrondensity in the void volume of compounds 92 and 94 that could not be appropriately modeled.The PLATON/SQUEEZE136 program was used to generate a data set free of electron densityin those regions. Crystallographic details for compounds 92-98 are listed in Table A.4 andTable A.5. Visualization of the solid state molecular structures was performed using Crystal-Maker?.3.3 Results and Discussion3.3.1 SynthesisThe synthesis of the oligothiophene dicarboxylic acids H23PhT2DC (67), H23HT2DC (68),H2T3DC (63), and H2Ph2T3DC (70) is described in Chapter 2. Dithienothiophene dicarboxylicacid (H2DTTDC, 91, Scheme 3.1) was formed from the condensation and cyclization of 2,5-dibromo-3,4-diformyl-thiophene with ethyl-2-mercaptoacetate followed by saponification andsubsequent acidification to give the dicarboxylic acid.693.3. Results and Discussion S S S CO2HHO2CS BrCHOBrOHC S S S CO2EtEtO 2CHSCH2CO2Et 2K 2CO3, DMF 1. LiOH, THF, 60 ?C2. HCl 9 1Scheme 3.1: Synthesis of 91Table 3.1: Summary of preparation and structure types for crystallographically characterizedcompounds 92?98.Compound PreparationDimen-sionalityNuclearity, geometryO2C?CO2modea92 Solvothermal 2D Mononuclear, octahedral f93 Liquid Diffusion 2D Binuclear, square pyramidal c94 Solvothermal 3D Linear trinuclear, octahedral c, g95 Liquid Diffusion 2D Binuclear, octahedral f96 Solvothermal 3D Mononuclear, octahedral c97Post-Solvothermal3D Mononuclear, octahedral h98 Solvothermal 1D Binuclear, octahedral eaChart 2.5.The synthesis of coordination polymers 92?98 are illustrated in Scheme 3.2. Crystals of 93were grown by liquid diffusion while compounds 92, 94?96 and 98 were synthesized directlyfrom solvothermal reactions. Solvothermal reaction times of 24 hours or less gave minimalproduct, and fast cooling rates (greater than 7.5 ?C hr?1) gave microcrystalline powder as theproduct. The low yield of compound 97 can be partially credited to most of the reactants beingconsumed in the formation of compound 96. The slow emergence of compound 97 from thereaction mixture of compound 96 is ascribed to the formation of a kinetic product, whereascompound 96 may be the thermodynamic product of the reaction. Table 3.1 summarizes thepreparation methods and structural aspects of compounds 92-98.3.3.2 Solid State Molecular StructuresPresenting a full description of the solid state molecular structures of these coordinationpolymers is imperative for the discussion of the magnetic properties in later sections. Under-standing the carboxylate binding modes aids in interpreting infrared spectroscopy data that isused to distinguish isomers 96 and 97. Comparisons will be drawn between the compoundsdiscussed below and the materials presented in Chapter 2. Selected bond lengths and angles703.3. Results and DiscussionS SHO2C S CO2HMnCl2   4 H2OS S CO2HHO2C S S CO2HHO2C PhPhC6H13C6H13 S SHO2C S CO2HPhPh96989492Post-solvothermal crystallization from mother liquor97Solvothermal conditionsCu(NO3)2    2.5 H2OCoCl2   6 H2O Layered diffusionS S S CO2HHO2C S S CO2HHO2C PhPh 9395++ Layered diffusionScheme 3.2: Synthesis of coordination polymers 92?98.713.3. Results and Discussionfor compounds 92?98 are listed in Table A.19?Table A.25.Bithiophene Coordination PolymersThe coordination environments of the synthesized bithienyl coordination polymers are il-lustrated in Chart 3.3. Compound 92 ([Mn(3PhT2DC)(DMF)0.45(H2O)2.55 ? 1.55 DMF]n forms2D sheets along the crystallographic ac plane. Each asymmetric unit (Figure 3.1a) contains 12Mn1, 12 Mn2, one 3PhT2DC2? linker, two coordinating H2O, one non-coordinating DMF, and adisordered site that is either coordinating water and non-coordinating DMF (55 % occupancy)or coordinating DMF (45 % occupancy). Both manganese sites adopt an octahedral geometry:Mn1 is coordinated to two trans monodentate carboxylates (O1) and four solvent molecules(H2O and DMF), while Mn2 is coordinated to four ?2-?1:?1 carboxylates (O3 and O4) and twosolvent molecules. Chart 2.5f shows the linker coordination of 3PhT2DC2? within 92. Syn?anti carboxylates bridge Mn2 centers to form Mn?carboxylate chains along the c-axis, andeach Mn2 is 4.52(1) ? from the nearest Mn2. Mn1 sites are not linked directly via carboxy-late bridges, and the distance between two Mn1 atoms is 9.04(2) ?. Mn1 effectively acts as abridge for the Mn2 nodes via 3PhT2DC2? linkers. The extended structure of 92 and the link-age of the manganese environments are shown in Figure 3.1b. The overall structure of 92 canbe reduced to a 4-connected uninodal net with sql-Shubnikov tetragonal plane net topology.The 3PhT2DC2? linker is twisted with a torsion angle of 122.49(2)?: the phenyl groups have acentroid-centroid distance of 6.96 ?, have a plane intersection angle of 81.5?, are flanked awayfrom each other and do not engage in intermolecular interactions. Non-coordinating solventand phenyl rings occupy the void space in the solid state structure.Liquid diffusion was used to grow crystals of 93, a Cu2+/3PhT2DC2? coordination polymerthat is isostructural to 74 (Figure A.3). Compound 93 belongs to the space group P2/n andhas thienyl torsion angles of S1-C5-C5-S1: -98.6(8)? and S2-C6-C6-S2: 46.1(8)?. The phenyl-phenyl centroid distances of 6.53 ? and 4.00 ? correlate to plane intersection angles of 88.9?and 24.0?, respectively. Although the phenyl rings in 93 are closer than in compounds 74, 77,and 80, they fail to reach the distance required for a genuine ??? interaction.178,179Overall, the three coordination polymers that contain 3PhT2DC2? as the sole linker (74, 92,and 93) are two-dimensional frameworks. Additionally, the mixed linker systems of 77 and80 are 1D and 2D systems, respectively. Literature precedent128,141 for the solid state structureof 3,3'-diphenyl-2,2'-bithiophene and its derivatives47 suggests that the conformations that areaccessible in the solid state will lead to 3PhT2DC2? having a linking angle 140-150?. Ligandswith such linking angles alone are not conducive to forming 3D frameworks.180 Additionally,723.3. Results and DiscussionS S CO2O2C PhPhOOOO MnDMFOOMnH2OH2OOH2 H2OOO OOOOn =DMF92 OOOOOO OOCuCuEtOHEtOH n S S CO2O2C PhPhOOOO =9 3 OOOO S S CO2O2C C6H13C6H13OOOO MnOOOO OOOOOOOOMnOH2OH2Mn OOOOOOOO H2ODMF =9 4Chart 3.3: Simplified coordination environments of compounds 92?94.733.3. Results and Discussiona)b)Figure 3.1: Solid state molecular structure of 92. a) Asymmetric unit of 92. Hydrogen atomshave been omitted for clarity. Thermal ellipsoids are shown at 50 % probability. b) Extendedview of 92 on the ac plane.the phenyl groups do not participate interactions such as inter-linker van der Waals contacts or? ? ? stacking that would direct the formation of a three-dimensional structure.A 3D framework belonging to the acentric orthorhombic space groupC2221 is formed uponcrystallization of [Mn6(3HT2DC)6(DMF)3(H2O)5 ? x DMF ? y H2O]n (94, Figure 3.2). Themetal nodes of 94 consist of linear trinuclear manganese centers coordinated to 3HT2DC2? link-ers, DMF, and H2O. Terminal-center manganese distances range from 3.702(3) ? to 3.748(3) ?.The four terminal manganese atoms in the asymmetric unit are coordinated to two solvent743.3. Results and Discussionmolecules each (Mn1, Mn4, and Mn6 are coordinated to a DMF and H2O, while Mn3 is co-ordinated to two H2O molecules), a ?2-?2:?1 carboxylate, and two ?2-?1:?1 carboxylates. Thecentral manganese atom is coordinated to six oxygens from six unique 3HT2DC2? linkers.Four of the oxygens belong to carboxylates that coordinate in a ?2-?1:?1 mode. The other twooxygens belong to carboxylates that bind in a ?2-?2:?1 fashion and coordinate to the terminalmanganese in addition to the central manganese atom. Mn?O bond lengths are typical: Mn?O carboxylate bond lengths range from 2.14-2.22 ?, while Mn?O solvate bond lengths rangefrom 2.06-2.27 ?. The six 3HT2DC2? within 94 have annular torsion angles near 55? and 90?.Previous theoretical studies calculate the torsion angle of 3,3'-dihexyl-2,2'-bithiophene to be72?,142 suggesting the n-hexyl chains will drive the thiophene rings of 3HT2DC2? to near per-pendicular angles. 3HT2DC2? adopts two coordination modes within the solid state structureof 94. Two linkers in the asymmetric unit have carboxylates that coordinate in a bis-bidentatefashion (Chart 2.5c) while the other four 3HT2DC2? linkers in the asymmetric unit coordinatewith a bidentate ?2-?1:?1 mode and a chelating-bridging ?2-?2:?1 mode (Chart 2.5g). The sixcoordinating 3HT2DC2? linkers bind to four other trinuclear metal nodes. As illustrated in Fig-ure 3.2, two 3HT2DC2? connect to two separate nodes, whereas two sets of two 3HT2DC2? actas a twisted double pillar and link to one node each.Compound 94 has a 4-connected uninodal lvt net topology and a Schla?fli symbol of 42.84when the trinuclear cluster is treated as a single node. n-Hexyl chains, some of which aredisordered, and non-coordinating solvent fill the voids of the coordination polymer. There is atleast one non-coordinating DMF in the asymmetric unit, but the exact number and compositionof solvent molecules could not be determined. The n-hexyl chains of the linkers are not evenlydistributed within the free space of 94 and appear to cluster within this structure. However,exact determination of the extent of aggregation cannot be assessed due to the disorder of the n-hexyl chains. Intraligand repulsion and interligand aliphatic attraction contribute to the twistingof the 3HT2DC2? linker and observed grouping of n-hexyl chains, which in turn influences theextended structure.The long-range configuration of 94 (Figure 3.2) is dissimilar to other bithienyl manganesecoordination polymers. Compound 92 has phenyl substituents at the thienyl beta positions andis a 2D sheet, whereas coordination polymer [Mn3(T2DC)3(DMF)4]n 124 (99), which containsthe unsubstituted bithiophene linker T2DC2?, has sxb topology and trinuclear centers that aresimilar to those in 94. Although the two compounds share inorganic building units, each trin-uclear center of 99 is linked to six other centers, whereas 94 is linked to four other centers.Figure 3.3a illustrates the simplified coordination of the trinuclear nodes for 94 and 99. Thischange in the linkage of the metal centers has a drastic effect on the overall topology. As il-753.3. Results and Discussiona)b)Figure 3.2: Solid state molecular structure of 94. a) Asymmetric unit; hydrogens, non-coordinating solvent, and n-hexyl chains have been omitted for clarity. Thermal ellipsoidsare shown at 50 % probability. b) Extended structure of 94 viewed from the bc plane.763.3. Results and Discussionlustrated in Figure 3.3b, the 4-connected lvt net topology of 94 is markedly different from the6-connected sxb topology of 99. The change in topology is attributed to van der Waals attrac-tion of the n-hexyl chains47,143 to other n-hexyl chains that directs the extended structure of 94.This interaction between chains causes the linkers to twist in a way that changes the linkingangle of the carboxylates which influences the position and orientation of metal centers.MnMnMnDMFDMFOOOOOOOOOOO ODMF DMFa)MnMnMnDMFOH2OOOOOOOOOOO ODMF H2Ob)c) d)Figure 3.3: Simplified coordination environments for the manganese trinuclear nodes of a) 6-connected [Mn3(T2DC)3(DMF)4]n (99); b) 4-connected compound 94. Colored rods illustratebithienyl linkers with rods of the same color going to the same trinuclear node. Net topologyof c) [Mn3(T2DC)3(DMF)4]n and d) 94.Terthiophene Coordination PolymersThe ?-terthiophene derivative T3DC2? has been previously used to form a copper metal-organic polyhedron with the T3DC2? linker in a cis,cis conformation and at a 90? linkingangle.127 A coordination polymer comprised DTTDC2? (91) and Ni2+ centers has been re-773.3. Results and DiscussionOOOO OOCoOH 2Copypy MeOHOOMeOH n95 S S S CO2O2COOOO SS S CO2O2COO OOOO OO OO OOOO OOOOOO OOOOOOMnMnOO OH 2H 2OH 2OMnOH 2Mn OOOO H 2OH 2O nOOOO MnMn Mn OO OODMFDMF OO DMFDMFOO OODMF DMF OOMnDMFDMF n OO S SO2C S CO2PhPhOO =S SO2C S CO2OO OO969798=== = MnH 2OH 2OChart 3.4: Simplified coordination environments of compounds 95?98.783.3. Results and Discussionported.181 In this section, the first crystallographically characterized structures of coordinationpolymers containing ?-terthiophene linkers are presented. Chart 3.4 illustrates the simplifiedcoordination environments of compounds 95?98.[Co(DTTDC)(C5H5N)(MeOH)(H2O)0.5 ? 2 MeOH]n (95, Figure 3.4) is isostructural to thereported Ni2+ analog with the exception of the identity of the coordinating solvent. The SBU isa binuclear center bridged by one carboxylate group and a water molecule. The Co?H2O?Coangle is 114.4(3)? and the metal centers are 3.557(6) ? apart. Co?O and Co?N distances areall typical with values between 2.04 ? and 2.12 ?. The carboxylates of DTTDC2? coordinateas shown in Chart 2.5f. One pyridine and one methanol each coordinate to the cobalt center togive an octahedral geometry around the metal, and the DTTDC2? linkers form 2D sheets.Reaction of MnCl2 ? 4 H2O and H2T3DC under solvothermal conditions affords two distinctproducts: compounds 96 ([Mn(T3DC)(H2O)2]n) and 97 ([Mn(T3DC)(H2O)1.5]n). Both are 3Dframeworks of Mn2+, T3DC2?, and coordinating H2O. The bulk material, 96, crystallizes in theacentric orthorhombic space group P212121. The asymmetric unit shown in Figure 3.5a con-tains one Mn2+, one T3DC2?, and two coordinating terminal water molecules. The carboxylateand water oxygens form an octahedral coordination environment around the manganese. TheT3DC2? linker adopts a ?2-?1:?1 (Chart 2.5c) binding mode. The syn-anti carboxylate-bridgedMn?Mn distances are 4.73(2) ? and 5.04(2) ?. The trans,cis thiophene rings of 96 are mod-erately coplanar: the S1-C5-C6-S2 torsion angle is 157.9(9)?, and the S2-C9-C10-S3 torsionangle is 19.8(9)?. The extended structure in Figure 3.5b and Figure 3.5c shows that the man-ganese centers form a 2D lattice that are connected by T3DC2? linkers along the c-axis. Whenthe manganese centers are treated as nodes, the simplified framework has a 4-connected lvttopology similar to 94.Crystals of 97were grown from the reaction mother liquor of 96. Compound 97 crystallizesin the monoclinic space group C2/c and is a 3D framework (Figure 3.6). The asymmetric unitconsists of one T3DC2? linker, oneMn2+, one coordinating terminal water molecule, and half ofa bridging water molecule. Figure 3.6a shows the asymmetric unit of 97. Two bis-monodentatecarboxylate oxygens (O1 and O2), a ?2:?2 carboxylate (O3 and O4), one terminal water, andone bridging water coordinate to the manganese center in an octahedral geometry. Chart 2.5hshows the T3DC2? coordination mode, and Figure 3.6c shows the simplified coordination en-vironment for the manganese center. The ?2-?2 Mn?O bond lengths are slightly elongated(2.199(5)?2.225(5) ?) compared to the bis-monodentate Mn?O bond (2.120(5)-2.144(5) ?).Similarly, the terminal H2O Mn?O bond is 2.157(5) ? compared to 2.262(4) ? for the bridg-ing H2O Mn-O bond. The manganese centers are rather close to each other with separationdistances of 3.379(7) ? and 3.731(7) ?.793.3. Results and Discussiona)b)Figure 3.4: a) Solid state molecular structure of 95. Non-O?H hydrogens and non-coordinatingsolvent have been removed for clarity. Thermal ellipsoids are shown at 50 % probability. b)Extended 2D structure of 95.The rings of the terthiophene linker of 97 are nearly coplanar. The S1-C5-C6-S2 torsionangle is 179.2(4)?, and the S2-C9-C10-S3 torsion angle is -178.8(4)? giving a trans,trans con-formation to the linker. The extended structure of 97 shows that the T3DC2? linkers are stackedin parallel pairs and are separated by 3.526(8) ? (S2-S2 contact) to 3.572(9) ? (terminal ringcentroid-centroid) (Figure 3.6b). These coplanar pairs arrange in a herringbone orientation803.3. Results and Discussiona)b)c)Figure 3.5: Solid state molecular structure of 96. a) The asymmetric unit of 96. Hydrogenshave been omitted for clarity. Thermal ellipsoids are shown at 50 % probability. b) View ofthe extended structure along the a axis. c) View of the carboxylate-bridged 2D lattice of Mn2+centers with terthiophene units removed for clarity.813.3. Results and Discussiona)b)MnH2OH2OO OOOMnOOOH2OOc) d)Figure 3.6: Solid state molecular structure of 97. a) Asymmetric unit; non O?H hydrogens havebeen omitted for clarity. Thermal ellipsoids are shown at 50 % probability. b) The extendedframework of 97. c) The simplified coordination environment of the manganese(II) center in97. d) Simplified topology of 97. Gray nodes: Mn2+; pink nodes: T3DC2?.823.3. Results and Discussionthroughout the coordination polymer. When the manganese(II) center and T3DC2? are treatedas nodes, the simplified framework has a 4-connected umc topology (Figure 3.6d) and is as-signed the Schla?fli symbol of 43.62.8.The stacking and orientations of 96, 97, and 2,2':5',2''-terthiophene (T3)182 differ from eachother in the solid state. T3 molecules crystallize in a herringbone orientation and do not engagein any close ?-? interaction. With respect to coplanarity, the thiophene rings of T3 deviate 6-9?,the rings in 96 are twisted by 20?, while 97 is the most planar. Similarly, sulfur-sulfur contacts,which can tune the redox and spectroscopic properties of a material,183,184 differ among thethree compounds. The closest S ? ? ? S contact is 3.70 ? for ?-terthiophene, 3.765(5) ? forS2 ? ? ? S2 of 96, and 3.526(2) ? for the S2 ? ? ? S2 contact of 97.These new terthiophene dicar-boxylate coordination polymers demonstrate the structural versatility of the T3DC2? linker.Reaction of phenyl-functionalized terthienyl linker H2Ph2T3DC (70) with a manganese(II)reagent gave coordination polymer [Mn(Ph2T3DC)(DMF)2]n (98). This coordination networkcrystallizes in the triclinic space group P1? and is comprised of 1D chains. Figure 3.7 showsthe metal center coordination as well as the extended structure of 98. The binding modes of98 are depicted in Chart 2.5e. The chains consist of alternating binuclear manganese clustersand two Ph2T3DC2? linkers, whereas zinc(II) analog compound 85 has mononuclear centersand one bridging molecule between metal centers. Two bis-monodentate carboxylate oxygens,two bidentate carboxylate oxygens, and two DMF molecules adopt a distorted octahedral ge-ometry around each crystallographically equivalent manganese center. The Mn?O distancesare 2.1296(9)-2.1367(9) ? for the monodentate carboxylate oxygens, 2.150(1)?2.163(1) ? forthe DMF oxygens, and 2.2339(9)?2.3322(9) ? for the bidentate carboxylate oxygens. Themanganese atoms in the binuclear cluster are separated by 4.505(2) ?.The cis,trans thiophene rings of 98 are less coplanar than those in compounds 85, 96,and 97: the S1-C5-C6-S2 torsion angle is 38.49(6)?, and the S2-C9-C10-S3 torsion angleis 150.35(7)?. Based on the C1-central thiophene centroid-C14 angle, the linking angle ofPh2T3DC2? deviates 40? from linearity. The twisted conformation of the linker in the solidstate and consequential dimensionality can be connected to the presence of the bulky phenylgroups at the beta position of the central thiophene ring and the binuclear SBU.Overall, compounds 92-98 demonstrate a sampling of the crystallographic environmentsavailable to oligothiophene derivatives within a coordination polymer. Although the oligoth-iophene ligands have similar linking angles, the presence of phenyl and n-hexyl functionalgroups control the dimensionality of the extended structures. In addition, compounds contain-ing terthiophene derivatives are not mere extensions of the bithiophene analogs. One strikingdifference between the bithiophene compound 99 and terthiophene compounds 96 and 97 is833.3. Results and Discussiona)b)Figure 3.7: Solid state molecular structure of 98. a) Asymmetric unit.; hydrogens have beenomitted for clarity. Thermal ellipsoids are shown at 50 % probability. b) Binuclear metalcenter.that the terthiophene compounds form rather dense frameworks lacking non-coordinating sol-vent.843.3. Results and Discussion3.3.3 PXRDThe phase purity of compounds 92?98 was determined using powder X-ray diffraction(PXRD). The diffraction patterns were compared to the predicted diffraction patterns from thestructure determined by single crystal X-ray crystallography (Figure B.15?Figure B.21). Forcompounds 92, and 95?98, the predicted and experimental powder patterns of the bulk materialmatch well. A prominent peak in the powder pattern of 93 is present around 2? = 8?, but theexperimental pattern matches the predicted pattern otherwise. Due to the small quantity of97 that was available for analysis, some peaks in the diffraction pattern of 97 are weaker thanexpected but still present. The peaks of the experimental diffraction pattern of 94 are broadcompared to the predicted pattern, and a loss of crystallinity is credited to structural collapseupon desolvation of the bulk material.3.3.4 Thermal StabilityThermogravimetric analysis (TGA) was performed on 92-96 and 98 to determine the ther-mal stability and evaluate the composition of these materials. A summary of the analyses isgiven in Table 3.2. Non-coordinated solvent is lost between 50 ?C and 120 ?C followed bythe loss of coordinating solvent near 200 ?C. Combustion of organic material occurs before400 ?C for one and two-dimensional coordination polymers 92 and 98 and by 450 ?C for three-dimensional frameworks 94 and 96. PXRD was used to determine the identify of the decom-position products for the manganese(II) compounds: a mixture of Mn3O4, MnOS, and traceamounts of other compounds that could not be identified were detected. As a consequence,theoretical final weight percents were not calculated.Table 3.2: Thermogravimetric data for selected compounds.Non-coordinated,adsorbed solvent(?C)Coordinatedsolvent (?C)Decomposition(?C)Final weight,experimental(%)92 50?120 140?205 275?390 15.394 60?90 95?260 320?465 18.496 90?110 175?200 295?425 33.998 80?100 165?250 340?400 34.0853.3. Results and Discussion3.3.5 Infrared SpectroscopyInfrared spectroscopy was used to confirm the carboxylate binding modes observed in man-ganese(II) coordination polymers.185 The results are summarized in Table 3.3. In compound 92,the weak C=O stretches anticipated for a non-coordinated oxygen belonging to a ?1 carboxylateare overwhelmed by the C=O stretch of DMF. The non-coordinated oxygen belonging to the?2:?2 carboxylate of 97 has distinct IR stretches at 1626 cm?1 and 1641 cm?1. These stretchesare absent in 96. Infrared spectroscopy was the best method for discerning microcrystallinesamples of 96 and 97.Table 3.3: IR stretching frequencies of manganese(II) compounds.CO2 ?asym CO2 ?sym C=O92 1347, 1410 1528, 1570 1637a94 1353, 1421 1530, 1565 1647a96 1380, 1439 1507, 1547 N/A97 1361, 1435, 1446 1509, 1530, 1557 1626, 1641b98 1379, 1441 1528, 1563 1639aa DMF. b ?2:?2 mode3.3.6 Magnetic SusceptibilityBulk magnetic susceptibilities of polycrystalline vacuum-dried samples of manganese com-pounds 92, 94, 96, and 98 were measured at 10 kOe in the temperature range of 2?300 K.Compound 97 could not be synthesized in sufficient quantities to perform magnetic suscepti-bility experiment. Non-linear regressions were performed to fit the experimental results to theappropriate models of magnetic susceptibility. The results of these experiments are shown inFigure 3.8 and Figure 3.9.Compound 92 consists of both isolated Mn2+ centers (Mn1) and and carboxylate-bridged1D Mn2+ chains (Mn2). Antiferromagnetic behavior, shown in Figure 3.8a, was observeddown to 2 K. At 300 K, the magnetic susceptibility is 3.91 cm3 K mol?1 which is less thanthe expected value of 4.37 cm3 K mol?1 for one isolated Mn2+ center.186 This deviation inthe magnetic susceptibility is due to the variation in solvation state from the calculated andactual solvation state of 92. A Curie constant of C = 4.18 cm3 mol?1 and a Weiss constant of? = ?8.57 K were found, suggesting intermolecular antiferromagnetic interactions are presentin the bulk material.863.3. Results and Discussion0 50 100 150 200 250 30000.20.40.60.8101234a)Temperature (K)? M(cm3mol?1) ?MT(cm3Kmol ?1)0 50 100 150 200 250 30000.20.40.60.81024681012b)Temperature (K)? M(cm3mol?1) ?MT(cm3Kmol ?1)Figure 3.8: ?M vs. T (?); ?MT vs. T (?) for a) 92; b) 94. The solid lines show the besttheoretical fit.873.3. Results and Discussion0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 000 . 0 50 . 10 . 1 50 . 20 . 2 50 . 3012345a)Temperature (K)? M(cm3mol?1) ?MT(cm3Kmol ?1)0 50 100 150 200 250 30000.10.20.30.40.50.60.702468b)Temperature (K)? M(cm3mol?1) ?MT(cm3Kmol ?1)Figure 3.9: ?M vs. T (?); ?MT vs. T (?) for a) 96; b) 98. The solid lines show the besttheoretical fit.883.3. Results and DiscussionThe distance between the carboxylate-bridged Mn2?Mn2 centers of 92 is 4.52(1) ?, whilethe Mn1?Mn1 centers are well separated by 9.04(2) ?. It can be assumed that there is in-significant interchain interaction or exchange between the Mn1 centers. The molar magneticsusceptibility of 92 can be modeled as?M =12(?chain + ?paramagnet) (3.1)where ?chain describes the Mn2?Mn2 interaction via the Fisher infinite chain model187 (Equa-tion 3.2):?chain =NAg2?2BS (S + 1)3kBT?1 + U1 ? U?(3.2)where NA is Avogardo?s number, ?2B is the Bohr magneton, S is nuclear spin, kB is Boltzmann?sconstant, T is temperature, U is the Langevin function:U = cothJS (S + 1)kBT?kBTS (S + 1)(3.3)and ?paramagnet (Equation 3.4) accounts for the contribution of the mononuclear Mn1 center:?paramagnet =NAg2?2BS (S + 1)3kBT(3.4)Applying this model to the experimental magnetic susceptibility data between 300 K and 10 Kgives g = 1.983(2) and J = ?2.00(3) cm?1 which confirms the antiferromagnetic behavior of92.At 300 K, the experimental ?MT value for 94 is 10.64 cm3 mol?1 K which is below the valueexpected for three isolated Mn2+ centers. The molecular weight used to calculate magneticsusceptibilities does not account for the non-coordinated solvent that could not be resolvedcrystallographically and may explain the large deviation of the experimental ?MT value fromthe expected value of 13.11 cm3 mol?1 K. Compound 94 adheres to the Curie-Weiss law downto 15 K, at which point ??1M deviates from linearity. The antiferromagnetic behavior of 94is demonstrated by a Curie constant of C = 11.60 cm3 mol?1 and a Weiss constant of ? =?17.00 K.The large distances between trinuclear clusters (12.86(3) ?) and the terminal manganesewithin a trinuclear cluster (7.43(2) ?) are presumed to negate any significant magnetic cou-pling: their interactions are assumed to be zero. Although the terminal manganese atoms are incrystallographically unique locations, the similar chemical environments and distances to the893.3. Results and Discussioncentral manganese atoms are sufficient grounds for treating the terminal manganese as equiva-lent species. Given these assumptions, the Hamiltonian for these trinuclear clusters is given inEquation 3.5:H? = ?2J(S? 1 ? S? 2 + S? 2 ? S? 3) (3.5)The appropriate energy terms188 are inserted into the van Vleck equation186 (Equation 3.6):?M =NAg2?2B3kBT??S (S + 1)(2S + 1)exp(?E/kBT )?(2S + 1)exp(?E/kBT )(3.6)whereE =JS (S + 1)2(3.7)per mole of metal ions. Modeling of the magnetic susceptibility data between 300 K and 15 Kgives values of g = 2.094(3) and J = ?2.88(3) cm?1 (Figure 3.8b). These values are similar tothose for other trinuclear manganese systems.189,190 Although 94 belongs to an acentric spacegroup, the magnetic behavior of the material does not reflect this crystallographic assignment.The lack of anisotropy or spin canting at low temperature can be associated with the loss ofacentricity upon removal from a solvent-rich environment. Structural collapse and a loss ofcrystallinity are observed in the bulk polycrystalline sample (Figure B.17).Compound 96 also crystallizes in an acentric space group and shows a significant deviationfrom normal antiferromagnetic behavior below 60 K. At 300 K, the experimental ?MT value is4.45 cm3 mol?1 K, which is slightly higher than expected for an isolated Mn2+ center. A Curieconstant of C = 5.18 cm3 mol?1 and Weiss constant of ? = ?43.03 K were found between60 K and 300 K indicating strong antiferromagnetic interactions within this temperature range(Figure 3.9a). Above 60 K, the magnetic coupling within the 2D lattice can be modeled usingEquation 3.8:?M =NAg2?2BS (S + 1)(1 + U)23kBT (1 ? U)2(3.8)where U is the previously defined Langevin function (Equation 3.3). Least-squares analysisof the magnetic susceptibility data gives g = 2.135(6) and J = ?1.94(3) cm?1 which confirmsthat the 2D sheets of metal centers are coupled antiferromagnetically.To help describe the change in magnetic behavior below 60 K, variable field magneticsusceptibilities were measured (Figure 3.10). At lower fields, ?MT increases slightly to a max-imum at 32 K before decreasing quickly again. This behavior is mostly saturated at 10 kOe.Below 25 K, saturation effects or antiferromagnetic interactions take over, and a minimumvalue of 0.50 cm3 K mol?1 is reached at 2 K. This behavior is attributed to spin canting191,192903.3. Results and Discussion10 20 30 4000.511.522.533.5a)100 Oe200 Oe500 Oe1000 Oe10000 OeTemperature (K)? MT(cm3Kmol?1)10 20 30 400.050.10.150.20.250.30.35b)Temperature (K)100 Oe200 Oe500 Oe1000 Oe10000 Oe? M(cm3mol?1)Figure 3.10: Low temperature magnetic susceptibility data for 96: ?MT vs. T (a) and ?Mvs. T (b) at various fields.913.3. Results and Discussion-40000 -20000 0 20000 40000-2-1012M(N?)H (Oe)Figure 3.11: Field dependence on the magnetization of 96 at 2 K.which is a common phenomenon for materials without an inversion center.167,168,193 Figure 3.11shows that no remnant magnetization is observed at 2 K, and the M vs. H curve does not in-crease rapidly at low field, suggesting that no ferromagnetic ordering is present at 2 K.To further elucidate the identity of the magnetic transition, zero-field cooled (ZFC) andfield cooled (FC) magnetic susceptibility data were collected at 100 Oe (Figure 3.12). Whilethe ?MT vs. T FC data shows a prominent feature in ?MT 20?40 K followed by a rapid decreaseupon further cooling, the ZFC cooled data shows monotonically decreasing values of ?MT be-tween 20 K and 40 K before decreasing rapidly. Divergence of the ZFC and FC data belowTc = 40 K demonstrates the irreversibility of the magnetic transition originating from a mag-netically ordered canted state. Convergence of magnetic susceptibility below 20 K suggeststhat antiferromagnetic interactions dominate in this regime.The plots of of ?M and ?MT vs. T for 98 are shown in Figure 3.9b. Upon coolingfrom 300 K, ?MT is 8.37 cm3 mol?1 K at 300 K, which is less than the expected value of8.74 cm3 mol?1 K for two isolated Mn2+ centers. The temperature dependence of ??1M obeys theCurie?Weiss law above 10 K with a Curie constant of C = 8.61 cm3 mol?1 and a Weiss constantof ? = ?5.14 K. The Hamiltonian for a homospin binuclear system186 is given in Equation 3.9:H? = ?JS? 1 ? S? 2 (3.9)923.3. Results and Discussion10 20 30 4000.511.522.533.5a)Temperature (K)? MT(cm3Kmol?1)FC 100 OeZFC 100 Oe10 20 30 400.050.10.150.20.250.30.35b)Temperature (K)? M(cm3mol?1) FC 100 OeZFC 100 OeFigure 3.12: FC and ZFC magnetization plots for 96: : ?MT vs. T (a) and ?M vs. T (b) at100 Oe.933.4. ConclusionsFor a binuclear system, the van Vleck equation (Equation 3.10) takes the form of:?M =2NAg2?2BkBT??S (S + 1)(2S + 1)exp(?E/kBT )?(2S + 1)exp(?E/kBT )(3.10)Following the Hamiltonian for a homospin binuclear system, least-squares analysis of the mag-netic susceptibility data gave g = 2.004(2) and J = ?0.594(5) cm?1, showing that the Mn2+ areweakly coupled through the carboxylate bridges of the binuclear cluster.3.4 ConclusionsA series of new bithiophene and terthiophene coordination polymers have been synthesizedand characterized. Compounds 96-98 are the first examples of crystallographically character-ized terthiophene coordination polymers. Compound 96 is the major product of the reactionof MnCl2 ? 4 H2O and H2T3DC under solvothermal conditions, while 97 crystallizes from thereaction mother liquor. Compound 93 is isostructural to the zinc(II) analog compound 74.Similar to 85, 98 forms 1D chains although the two compounds have different metal centercoordination environments and planarity of the terthiophene backbone. This work has shownthat alkyl chains cluster in the otherwise void space of the coordination polymers. These in-teractions cause the thiophene rings to twist to near perpendicular angles and help to shape thetopology of the extended structure. Similarly, phenyl groups do not provide any driving forcefor forming a particular extended structure and cause the linker to have the wrong geometry forforming 3D frameworks. The magnetic behavior of the manganese coordination polymers aresensitive to both the short range and extended structure. Compounds 92, 94, 96, and 98 exhibitantiferromagnetic behavior and are well modeled by the given equations that describe the coor-dination environments. A spin-canting transition is present in noncentrosymmetric compound96 but is not observed in compound 94 due to a proposed structural collapse in the framework.94Chapter 4Gold(I) Cyclic Trinuclear Complexes4.1 IntroductionCoinage metal cyclic trinuclear complexes (CTCs) are nine-membered systems composedof copper, silver, or gold ions bridged by (C,N) or (N,N) linkers such as pyridinates, carbe-nates, triazolates, imidalozates, and pyrazolates.79,194 This class of materials has been widelystudied over the past 30 years for basic science research and applications in device fabri-cation.85,90,195,196 The potential uses of CTCs include metal-organic light emitting diodes,197biomedical applications,198 liquid crystals,90,91 and as building units in metal-organic frame-works.88,89Intermolecular metal-metal interactions, known as metallophilic interactions,199 are oftenpresent in coinage metal CTCs and are integral in determining the structure and electronicbehavior of these compounds. For gold(I) atoms, aurophilic interactions originate from filled5d orbitals and empty 6s and 6p orbitals, are akin to strong van der Waals forces,199 and can aidthe formation of oligomeric or extended polymeric species. For example, [AuPz]3 (40, Section1.3) forms dimeric pairs with an intermolecular Au?Au distance of 3.31 ?. An interdimericAu?Au contact of 3.16 ? occurs between nearly orthogonal pairs with a plane intersectionangle of 77.7?. Considering both the intradimeric and interdimeric aurophilic interactions,compound 40 exists as a coordination polymer. In addition, aurophilic-based phosphorescenceis observed at room temperature in the solid state for compound 40.85Upon absorption of a photon, coinage metal cyclic trinuclear complexes can relax via ra-diative or non-radiative pathways as shown in Figure 4.1. Excitation of a coinage metal CTCinto the S1 state can give singlet emission arising from the ligand, metal, or mixed metal-ligandstate. If fluorescence or another non-radiative decay process does not occur, intersystem cross-ing (ISC) to a triplet excited state can cause phosphorescence that originates from the ligand,metal ion, metallophilic interaction of a dimeric species, mixed ligand-metal, or metal per-turbed ligand-based state.93,95 Heavy metal ions such as gold(I) promote intersystem crossingthrough spin-orbit coupling and sensitization of ligand-based phosphorescence.200?202 Emis-sion from metal or metallophilic-based molecular orbitals have broad and unstructured spec-954.1. IntroductionEnergyS0S1EmissionISCT1Nonradiative decayEmissionFigure 4.1: Jablonski diagram illustrating some accessible decay pathways within cyclic trinu-clear complexes.tra, and multiple emitting states may be present depending on the temperature and electronicstructure of the complex. Pyrazole-contributing emission, either singlet or triplet, possessesstructured vibronic bands spaced ?1400 cm?1 apart. Emission lifetime measurements andcomputational modeling aid in assigning photoluminescent transitions.The Stokes shift of metallophilic emission is generally on the order of 13,000?20,000 cm?1because of the significant geometric distortion between the singlet and triplet excited states.82,92Theoretical studies of a dimeric unit of compound 40, {[Au(Pz)]3}2, suggest an interplanar con-traction of 0.7 ? coincides with expansion of the horizontal distance.93 Experimental studiesof {[Cu(Pz)]3}2 confirm that an intermolecular contraction of 0.65 ? occurs in the triplet state.Few examples of CTCs with extended conjugated groups have been reported. Pressuredependent PXRD and luminescence studies were performed to draw relations between in-termolecular metallophilic interactions and luminescent properties of copper(I) 3,5-dimethylpyrazolates containing phenyl (100), napthyl (101), and anthryl (102) moieties.203 Pressure-induced intermolecular compression of all three compounds was observed through changesin the interplanar spacing seen in PXRD powder patterns. Enhancement of phosphorescenceintensity at increased pressure was observed for compounds 100 and 101, while the > 6 ?Cu?Cu distance for compound 102 prohibits an enhancement of intermolecular metallophilicluminescence.Cyclic trinuclear complexes containing thiophene groups may be suitable for electropoly-merization to form conductive thin films. Oligothiophenes containing gold(I) ions have beenelectropolymerized and previously reported. Monomers of a gold(I) N-heterocyclic carbenecomplex with bithiophene moieties form 1D coordination polymers in the solid state with Au?Au contacts of 3.2262(4) ?.204 Electropolymerization via ?-bithienyl linkages gives compound964.1. IntroductionN N CuCuN NN Cu N RR R R = 1 0 01 0 11 0 2Chart 4.1: Structures of 100?102. Ref.203103 which exhibits good conductivity properties. UV-Vis absorption studies support the dom-inance of ?-?? transitions in the electronic structure of 103. An alkynethiolate gold(I) linearmetallopolymer (104) has a lower oxidation potential and stronger electron donor charactercompared to the parent monomer.205 This behavior indicates the polymer is more conjugatedthan the monomer. Previous synthetic efforts in the Wolf group resulted in electropolymerizedmaterials containing 3,3'-diethynyl-2,2':5',2''-terthiophene, pendant gold(I) groups, and triph-enylphosphine (105), CN? (106), or diphenylphosphinomethane (dppm) (107) groups.206 Thebridging dppm unit within the monomer of compound 107 forces an Au?Au contact length of3.20 ?. This interaction does not cause twisting of the terthiophene backbone and the materialis still suitable for electropolymerization. Cyclic voltammograms of 107 suggest a Au+/Au2+redox couple supported by aurophilic interactions is present.This chapter sets out to establish the relationship between the structure of bridging thienylpyrazolates within gold(I) cyclic trinuclear complexes and the photoluminescent propertiesof these compounds. Computational methods are used to support the assignment of metal-perturbed ligand-based phosphorescence frommonothienyl complexes, while low lying ligand-based LUMOs present in bithienyl systems prohibit metal sensitized phosphorescence. Sol-uble n-hexyl derivatives have been synthesized to explore the electrochemical properties ofgold(I) thienyl pyrazolates CTCs, and characterization of electropolymerized thin films wasconducted.974.2. ExperimentalN NCS Sn -Bu n -BuSS nAuCl S S Au S S n n-S SS AuXAuX n103 104105106107X = dppm PPh3CN -Chart 4.2: Structures of 103?107. Ref.204?2064.2 Experimental4.2.1 General3-Hexylthiophene, 2,2'-bithiophene-5-boronic acid pinacol ester, 1-Boc-pyrazole-4-boronicacid pinacol ester, 1-Boc-3,5-dimethyl pyrazole-4-boronic acid pinacol ester, tetrabutylammo-nium hexafluorophosphate ([n-Bu4N][PF6]), and [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (PEPPSI-IPr) were purchased from SigmaAldrich. Tetrakis(triphenylphosphine)palladium(0) (Pd(PPh3)4) was purchased from StremChemicals. 2-Thienylboronic acid was purchased from Maybridge. THF was purchased fromOmniSolve. Triethylamine was purchased from Fisher Scientific. All chemicals were usedas received. AuCl(tht) (tht = tetrahydrothiophene),207 2-bromo-3-hexylthiophene,208 and 5-bromo-3,3'-dihexyl-2,2'-bithiophene208 were prepared according to literature procedures. Syn-theses of 4-iodo-1-[(4-methylphenyl)sulfonyl]-1H-pyrazole (108) and 3,5-dimethyl-4-iodo-1-[(4-methylphenyl)sulfonyl]-1H-pyrazole (109) were modified from literature procedure:209 io-dinated precursors were used instead of brominated precursors.1H and 13C NMR spectra were collected on a Bruker AV-300 or AV-400 spectrometer andwere referenced to residual solvent: CDCl3, 7.27 ppm (1H), 77.0 ppm (13C); Acetone-d6, 2.05ppm, 29.8 ppm; CD2Cl2, 5.32 ppm (1H), 53.8 ppm (13C). UV-Vis absorption spectra werecollected using a Varian Cary 5000 spectrometer. Emission and excitation spectra were ob-tained on a Photon Technology International fluorimeter using a 75 W arc lamp as a source and984.2. Experimentalwere uncorrected for lamp intensity. Low temperature emission spectra were obtained fromtoluene solutions using an Oxford OptistatDN cryostat. EI mass spectra were obtained usinga Kratos MS-50 mass spectrometer coupled to a MASPEC data system. MALDI-TOF massspectra were obtained on a Bruker Biflex IV MALDI-TOF instrument equipped with a nitrogenlaser. CHN elemental analyses were performed using a EA1108 elemental analyzer. Infraredspectra were obtained on a Thermo Nicolet 6700 with a Smart Orbit accessory in the range of4000-400 cm?1. X-ray photoelectron spectroscopy (XPS) analysis was performed using a Ley-bold MAX200 spectrometer equipped with an aluminum K? source. Cyclic voltammetry wasperformed on a Pine potentiostat with either a glassy carbon or indium tin oxide (ITO) work-ing electrode, silver/silver ion non-aqueous reference electrode, and platinum mesh counterelectrode at room temperature (20 ? 23 ?C). Decamethylferrocene was used as an internal ref-erence. Tetrabutylammonium hexafluorophosphate ([n-Bu4N][PF6]) was recrystallized threetimes from ethanol and heated to 80 ?C for three days prior to use. Solutions used for cyclicvoltammetry contained 0.1 M [n-Bu4N][PF6] and 1 ? 10?3 M analyte. Cyclic voltammetry wascarried out in CH2Cl2 dried over an activated alumina column.4.2.2 Procedures1-[(4-Methylphenyl)sulfonyl]-4-(2-thienyl)-1H-pyrazole (110):A degassed 2:1 THF/water (24 mL) solution of K2CO3 (0.304 g, 2.20 mmol), 2-thienylboronic acid (0.128 g, 1.00 mmol), 108 (0.347 g, 1.00 mmol), and Pd(PPh3)4 (0.0648 g,0.0560 mmol) was heated to reflux for 16 hours. The reaction mixture was cooled to roomtemperature and most of the THF was removed in vacuo. CH2Cl2 (20 mL) was added to theresulting mixture and was washed with H2O (3 ? 10 mL). The organic layer was dried overMgSO4, filtered, and the solvent was removed in vacuo to give an orange solid. The crudeproduct was purified via column chromatography on silica gel with CH2Cl2 as the eluent togive a white solid in 70 % yield. m/z: 304. 1H NMR (300 MHz, CDCl3): ? 8.24 (s, 1H), 7.93(d, J = 9 Hz, 2 H), 7.89 (s, 1H), 7.35 (d, J = 8 Hz, 2H), 7.25 (dd, J = 1 Hz, J = 8 Hz, 1 H), 7.14(dd, J = 1 Hz, J = 3 Hz, 1H), 7.04 (dd, J = 3 Hz, J = 8 Hz), 2.43 (s, 3H).3,5-Dimethyl-1-[(4-methylphenyl)sulfonyl]-4-(2-thienyl)-1H-pyrazole (111):A procedure similar to that used for the synthesis of 110 was used with reagents K2CO3(0.304 g, 2.20 mmol), 2-thienyl boronic acid (0.128 g, 1.00 mmol), 109 (0.376 g, 1.00 mmol),994.2. Experimentaland Pd(PPh3)4 (0.058 g, 0.050 mmol) to give an orange solid. The crude product was purifiedvia column chromatography on silica with CH2Cl2 as the eluent to give a white solid in 69 %yield. m/z: 332. 1H NMR (300 MHz, CDCl3): ? 7.90 (d, J = 8 Hz, 2H), 7.35 (m, 3H), 7.09 (dd,J = 3 Hz, J = 5 Hz), 6.91 (dd, J = 1 Hz, J = 3 Hz), 2.57 (s, 3H), 2.44 (s, 3H), 2.27 (s, 3H).4-[5-(2,2'-Bithiophene)]-1-[(4-methylphenyl)sulfonyl]-1H-pyrazole (112):A procedure similar to that used for the synthesis of 110 was used with reagents K2CO3(0.304 g, 2.20 mmol), 2,2'-bithiophene-5 boronic acid pinacol ester (0.292 g, 1.00 mmol), 108(0.348 g, 1.00 mmol), and Pd(PPh3)4 (0.058 g, 0.050 mmol) to give an orange solid. The crudeproduct was purified via column chromatography on silica with CH2Cl2 as the eluent to give alight yellow solid in 51 % yield. m/z: 386. 1H NMR (300 MHz, CDCl3): ? 8.23 (s, 1H), 7.93(d, J = 8 Hz, 2H), 7.89 (s, 1H), 7.35 (d, J = 8 Hz, 2H), 7.23 (dd, J = 1 Hz, 5 Hz), 7.16 (dd, J =1 Hz, J = 3 Hz, 1H), 7.09 (d, J = 1 Hz, J = 7 Hz, 1H), 7.05 (m, 2H), 2.44 (s, 3H).4-[5-(2,2'-Bithiophene)]-3,5-dimethyl-1-[(4-methylphenyl)sulfonyl]-1H-pyrazole (113):A procedure similar to that used for the synthesis of 110 was used with reagents K2CO3(0.304 g, 2.20 mmol), 2,2'-bithiophene-5 boronic acid pinacol ester (0.292 g, 1.00 mmol), 109(0.376 g, 1.00 mmol), and Pd(PPh3)4 (0.058 g, 0.050 mmol) to give an orange solid. The crudeproduct was purified via column chromatography on silica with CH2Cl2 as the eluent to give alight yellow solid in 49 % yield. m/z: 414. 1H NMR (300 MHz, CDCl3): ? 7.91 (d, J = 8 Hz,2H), 7.35 (d, J = 8 Hz, 2H), 7.23 (dd, J = 1 Hz, 5 Hz), 7.16 (dd, J = 1 Hz, J = 3 Hz, 1H), 7,14(d, 3 Hz, 1H), 7.02 (dd, J = 3 Hz, J = 5 Hz, 1H), 6.81 (d, J = 3 Hz, 1H), 7.09 (d, J = 1 Hz, J =7 Hz, 1H), 2.60 (s, 3H), 2.44 (s, 3H), 2.30 (s, 3H).1-Boc-4-[2-(3-hexylthienyl)]-1H-pyrazole (114):A degassed 3:1 THF/water (20 mL) solution of K2CO3 (0.304 g, 2.20 mmol), 2-bromo-3-hexylthiophene (0.247 g, 1.00 mmol), 1-Boc-pyrazole-4-boronic acid pinacol ester (0.294 g,1.00 mmol), and PEPPSI-IPr (0.0340 g, 0.0500 mmol) was heated to 50 ?C for one day. Thereaction mixture was cooled to room temperature and most of the THF was removed in vacuo.CH2Cl2 (20 mL) was added to the resulting mixture and was washed with H2O (3 ? 10 mL).The organic layer was dried over MgSO4, filtered, and the solvent was removed evaporatedin vacuo to give a brown oil. The crude product was purified via column chromatography on1004.2. Experimentalsilica gel with CH2Cl2 (with 0.1 % triethylamine) as the eluent giving a light yellow oil in 52 %yield. m/z: 334. 1H NMR (300 MHz, CDCl3): ? 8.14 (s, 1H), 7.83 (s, 1H), 7.19 (d, J = 5 Hz,1H), 6.95 (d, J = 5 Hz, 1H), 2.65 (t, J = 8 Hz, 2H), 1.69 (s, 9H), 1.58 (m, 2H), 1.31 (m, 6H),0.88 (t, J = 7 Hz, 3 H).1-Boc-3,5-dimethyl-4-[2-(3-hexylthienyl)]-1H-pyrazole (115):A procedure similar to that used for the synthesis of 114 was used with reagents K2CO3(0.304 g, 2.20 mmol), 2-bromo-3-hexylthiophene (0.247 g, 1.00 mmol), 1-Boc-3,5-dimeth-yl-pyrazole-4-boronic acid pinacol ester (0.322 g, 1.00 mmol), and PEPPSI-IPr (0.0340 g,0.0500 mmol) to give a brown oil. The crude product was purified via column chromatographyon silica gel with CH2Cl2 (with 0.1 % triethylamine) as the eluent giving a light yellow oil in44 % yield. m/z: 362. 1H NMR (300 MHz, CDCl3): ? 7.30 (d, J = 5 Hz, 1H), 6.99 (d, J = 5 Hz,1H), 2.36 (s, 3H), 2.34 (t, J = 8 Hz, 2H), 2.17 (s, 3H), 1.63 (s, 9H), 1.47 (m, 2H), 1.20 (m, 6H),0.85 (t, J = 7 Hz, 3H).1-Boc-4-[5-(3,3'-dihexyl-2,2'-bithienyl)]-1H-pyrazole (116):A procedure similar to that used for the synthesis of 114 was used with reagents K2CO3(0.304 g, 2.20 mmol), 5-bromo-3,3'-dihexyl-2,2'-bithiophene (0.413 g, 1.00 mmol), 1-Boc-pyrazole-4-boronic acid pinacol ester (0.294 g, 1.00 mmol), and PEPPSI-IPr (0.0340 g,0.0500 mmol) to give a brown oil. The crude product was purified via column chromatog-raphy on silica gel with CH2Cl2 (with 0.1 % triethylamine) as the eluent giving a light yellowoil in 38 % yield. m/z: 500. 1H NMR (300 MHz, CDCl3): ? 8.20 (s, 1H), 7.90 (s, 1H), 7.31 (d,J = 5 Hz, 1H), 7.04 (s, 1H), 6.97 (d, J = 5 Hz, 1H), 2.54 (t, J = 8 Hz, 2H), 2.48 (t, J = 8 Hz,2H), 1.68 (s, 9H), 1.56 (m, 4H), 1.23 (m, 12H), 0.86 (m, 6H).1-Boc-4-[5-(3,3'-dihexyl-2,2'-bithienyl)]-3,5-dimethyl-1H-pyrazole (117):A procedure similar to that used for the synthesis of 114 was used with reagents K2CO3(0.304 g, 2.20 mmol), 5-bromo-3,3'-dihexyl-2,2'-bithiophene (0.413 g, 1.00 mmol), 1-Boc-3,5-dimethyl-pyrazole-4-boronic acid pinacol ester (0.322 g, 1.00 mmol), and PEPPSI-IPr(0.0340 g, 0.0500 mmol) to give a brown oil. The crude product was purified via columnchromatography on silica gel with CH2Cl2 (with 0.1 % triethylamine) as the eluent giving alight yellow oil in 36 % yield. m/z: 528. 1H NMR (300 MHz, CDCl3): ? 7.30 (d, J = 5 Hz,1014.2. Experimental1H), 6.98 (d, J = 5 Hz, 1H), 6.80 (s, 1H), 2.61 (s, 3H), 2.58 (t, J = 8 Hz, 2H), 2.53 (t, J = 8 Hz,2H), 2.37 (s, 3H), 1.67 (s, 9H), 1.57 (m, 4H), 1.27 (m, 12H), 0.86 (m, 6H).4-(2-Thienyl)-1H-pyrazole (118):Compound 110 (0.152 g, 0.500 mmol) was added to 2:1 MeOH/5 M NaOH (6 mL). Themixture was refluxed for five hours. Upon cooling the reaction mixture to room temperature,the reaction volume was reduced by half, 15 mL of CH2Cl2 was added, and the organic layerwas washed with (4 ? 6 mL). The organic layer was dried over MgSO4, filtered, and driedin vacuo to give a white solid in 88 % yield. Crystals suitable for SCXRD were grown fromslow evaporation of CH2Cl2 to give colorless crystals of 118. m/z: 150. 1H NMR (400 MHz,Acetone-d6): ? 11.86 (s, 1H), 7.88 (s, 2H), 7.27 (dd, 1 Hz, 5 Hz, 1H), 7.18 (dd, 1 Hz, 3 Hz,1H), 7.03 (dd, 3 Hz, 5 Hz, 1H). 13C NMR (100 MHz, Acetone-d6): ? 137.2, 137.0, 128.9,124.1, 124.0, 123.6. FT-IR (cm?1): 3101 (m, br), 2930 (m, br), 2840 (w, br), 1589 (w), 1516(w), 1494 (w), 1434 (w), 1386 (w), 1346 (m), 1213 (m), 1148 (m), 1045 (w), 1018 (m), 950(m), 908 (w), 855 (m), 840 (s), 808 (s), 688 (vs), 657 (s), 619 (s), 576 (m), 559 (w), 498 (m),405 (m) Elem Calc for C7H6N2S: C, 55.98; H, 4.03; N, 18.65. Found: C, 55.51; H, 4.16; N,17.85.3,5-Dimethyl-4-(2-thienyl)-1H-pyrazole (119):A procedure similar to that used for the synthesis of 118 was used with compound 109(0.199 g, 0.600 mmol). A white solid was obtained in 93 % yield. Crystals suitable forSCXRD were grown from layering hexanes on a solution of 119 in CH2Cl2. m/z: 178. 1HNMR (400 MHz, Acetone-d6): ? 11.59 (s, 1H), 7.38 (dd, J = 1 Hz, J = 6 Hz, 1H), 7.10 (dd, J= 3 Hz, J = 5 Hz, 1H), 6.99 (dd, J = 1 Hz, J = 6 Hz, 1H), 2.31 (s, 6H). 13C NMR (100 MHz,Acetone-d6): ? 132.2, 128.7, 125.3, 124.5, 122.0, 113.7, 30.0. FT-IR (cm?1: 3156 (w, br), 3101(m), 3063 (m), 3020 (m), 2921 (m, br), 2829 (m, br), 1588 (w), 1550 (m), 1496 (w), 1433 (m),1415 (m), 1304 (q), 1249 (m), 1209 (w), 1157 (w), 1053 (w), 1034 (m), 1002 (w), 942 (m),819 (m, br), 698 (s), 686 (s), 631 (m), 587 (w), 517 (m), 476 (w). Calc for C9H10N2S: C, 60.64;H, 5.65; N, 15.72. Found: C, 60.63; H, 5.53; N, 15.65.4-[5-(2,2'-Bithienyl)]-1H-pyrazole (120):A procedure similar to that used for the synthesis of 118 was used with compound 1121024.2. Experimental(0.154 g, 0.400 mmol), and 30 mL CH2Cl2 was used to extract 120. The crude product waswas via centrifugation thrice in 1:1 CH2Cl2/hexanes to gives a yellow solid in 92 % yield. m/z:232. 1H NMR (Acetone-d6): ? 7.93 (s, 2H), 7.39 (d, J = 5 Hz, 1H), 7.24 (d, J = 3 Hz, 1H),7.18 (d, J = 4 Hz, 1H), 7.14 (d, J = 4 Hz, 1H), 7.07 (dd, J = 3 Hz, J = 5 Hz, 1H). 13C NMR(100 MHz, Acetone-d6): 135.5, 133,7, 129.0, 126.6, 126.2, 125.3, 124.3, 124.1, 123.1. ? FT-IR (cm?1): 3103 (m, br), 2927 (m, br), 1513 (m), 1427 (m), 1381 (m), 1348 (m), 1331 (w),1197 (w), 1145 (m), 1045 (w), 1014 (m), 950 (m), 909 (w), 862 (w), 835 (s), 818 (w), 796 (vs),700 (s), 658 (m), 623 (m), 541 (m), 479 (m). Elem Calcd for C11H8N2S2: C, 56.87; H, 3.47;N, 12.06. Found C, 56.52; H, 11.70; N, 3.52.4-[5-(2,2'-Bithienyl)]-3,5-dimethyl-1H-pyrazole (121):A procedure similar to that used for the synthesis of 118 was used with compound 113(0.166 g, 0.400 mmol), and 30 mL CH2Cl2 was used to extract 121. The crude product waswas via centrifugation thrice in 1:1 CH2Cl2/hexanes to gives a yellow solid in 89 % yield. m/z:260. 1H NMR (400 MHz, Acetone-d6) ? 11.64 (s, 1H), 7.39 (dd, J = 1 Hz, J = 6 Hz, 7.27 (dd,J = 1 Hz, J = 6 Hz, 1 H), 7.24 (d, J = 5 Hz, 1H), 7.07 (dd, J = 3 Hz, J = 5 Hz, 1H), 6.95 (d,J = 4 Hz, 1H), 2.36 (s, 6H). 13C NMR (100 MHz, Acetone-d6): ? 136.5, 135.9, 129.7, 129.0,126.1, 125.3, 125.0, 124.2, 124.0, 111.6, 30.2. FT-IR (cm?1): 3055 (m, br), 2917 (m, br), 1581(m), 1553 (w), 1521 (m), 1452 (w), 1413 (m), 1378 (w), 1298 (m), 1256 (m), 1219 (w), 1149(w), 1034 (m), 1007 (w), 979 (w), 944 (m), 881 (w), 831 (m), 796 (vs), 779 (s), 686 (vs), 637(m), 575 (w), 542 (m), 502 (w), 474 (m), 427 (m). Elem Calc for C13H12N2S2: C, 59.97; H,4.65; N, 10.76. Found: C, 59.85; H, 4.51; N, 10.46.4-[2-(3-Hexylthienyl)]-1H-pyrazole (122):Compound 114 (0.167 g, 0.500 mmol) was dissolved in 2:1 MeOH/4 M HCl (6 mL) andheated to 60 ?C for two hours. Upon cooling the reaction mixture to room temperature, thevolume was reduced by half, 8 mL of CH2Cl2 was added, and the organic layer was washedwith H2O (4 ? 5 mL). The organic layer was dried over MgSO4, filtered, and dried in vacuo togive a yellow oil in 89 % yield. m/z: 234. 1H NMR (400 MHz, CDCl3): ? 7.76 (s, 2H), 7.15(d, 5 Hz, 1H), 6.95 (d, 5 Hz, 1H), 2.65 (t, 8 Hz, 2H), 1.62 (m, 2H), 1.29 (m, 6H), 0.88 (t, J= 7 Hz, 3H). 13C NMR (100 MHz, CDCl3): ? 147.6, 138.8, 133.0, 129.5, 122.7, 119.0, 31.7,30.6, 29.2, 29.0, 22.6, 14.1. FT-IR (cm?1): 3160 (m, br), 2953 (s), 2923 (vs), 2854 (s), 1592(w), 1464 (m), 1367 (m), 1259 (w), 1144 (m), 1067 (w), 1023 (s), 947 (m), 912 (m), 855 (m),1034.2. Experimental836 (w), 799 (m), 721 (w), 662 (m), 625 (m), 505 (m). Elem Calc for C13H18N2S: C, 66.62; H,7.74; N, 11.95. Found: C, 65.45; H, 8.36; N, 11.28.4-[2-(3-Hexylthienyl)]-3,5-dimethyl-1H-pyrazole (123):A procedure similar to that used for the synthesis of 122 was used with compound 115(0.152 g, 0.420 mmol). A yellow oil was obtained in 92 % yield. m/z: 262. 1H NMR (400MHz,CD2Cl2) ? 9.67 (s, 1H), 7.28 (d, J = 5 Hz, 1H), 7.02 (d, J = 5 Hz, 1H), 2.40 (t, J = 7 Hz, 2H),2.20 (s, 6H), 1.51 (m, 2H), 1.21 (m, 6H), 0.84 (t, J = 7 Hz, 3H). 13C (100 MHz, CD2Cl2):? 144.3, 141.9, 129.1, 128.6, 125.0 111.1, 32.2, 31.1, 29.6, 29.1, 23.2, 14.4, 11.6. FT-IR(cm?1): 3172 (m), 3127 (w), 3063 (w), 2953 (s), 2922 (vs), 2854 (s), 1596 (w), 1553 (w), 1455(m), 1376 (m), 1307 (m), 1259 (w), 1154 (m), 1042 (m), 1000 (w), 834 (m), 777 (m), 718 (s),686 (m), 653 (m), 531 (m), 457 (w). Elem Calc for C15H22N2S: C, 68.66; H, 8.45; N, 10.68.Found: C, 67.57; H, 8.59; N, 11.14.4-[5-(3,3'-Dihexyl-2,2'-bithienyl)]-1H-pyrazole (124):A procedure similar to that used for the synthesis of 122 was used with compound 116(0.175 g, 0.350 mmol). A yellow oil was obtained in 82 % yield. m/z: 400. 1H NMR (400MHz,CDCl3) ? 7.82 (s, 2H), 7.30 (d, J = 5 Hz, 1H), 6.98 (s, 1H), 6.97 (d, J = 5 Hz, 1H), 2.55 (t,J = 8 Hz, 2H), 2.49 (t, J = 8 Hz, 2H), 1.56 (m, 4H), 1.25 (m, 12H), 0.86 (m, 6H). 13C NMR(100 MHz, CDCl3): ? 143.1, 142.4, 135.4, 131.0, 128.6, 128.5, 126.7, 125.3, 124.5, 123.1,31.6, 30.7, 30.6, 29.7, 29.1, 29.0, 28.9, 28.8, 22.6, 14.1. FT-IR (cm?1): 2955 (m), 2921 (s),2852 (s), 1588 (m), 1521 (w), 1456 (m), 1372 (m),1260 (s), 1196 (w), 1094 (s), 1040 (s), 1020(s), 873 (w), 818 (s), 801 (s), 692 (m), 641 (m). Elem Calc for C23H32N2S2: C, 68.95; H, 8.05;N, 6.99. Found: C, 68.73; H, 8.21; N, 7.15.4-[5-(3,3'-Dihexyl-2,2'-bithienyl)]-3,5-dimethyl-1H-pyrazole (125):A procedure similar to that used for the synthesis of 122 was used with compound 117(0.158 g, 0.300 mmol). A yellow oil was obtained in 87 % yield. m/z: 428. 1H NMR (400MHz,CDCl3) ? 7.29 (d, J = 5 Hz, 1H), 6.97 (d, J = 5 Hz, 1H), 6.83 (s, 1H), 2.56 (t, J = 8 Hz, 2H),2.52 (t, J = 8 Hz, 2H), 2.43 (s, 6H), 1.57 (m, 4H), 1.28 (m, 12H), 0.86 (m, 6H). 13C NMR(100 MHz, CDCl3): ? 142.5, 142.4, 142.3, 136.3, 134.7, 127.4, 126.5, 125.3, 124.0, 31.6,30.7, 30.2, 29.7, 29.1, 29.0, 28.9, 28.8, 22.6, 14.0, 12.2. FT-IR (cm?1): 3188 (w), 3064 (w),1044.2. Experimental2954 (s), 2922 (vs), 2853 (s), 1586 (w), 1539 (w), 1509 (w), 1456 (m), 1415 (w), 1377 (m),1303 (w), 1261 (m), 1157 (w), 1086 (m), 1014 (m), 833 (m), 798 (s), 738 (s), 660 (w). ElemCalc for C25H36N2S2: C, 70.04; H, 8.46; N, 6.53. Found: C, 70.36; H, 8.81; N, 6.22.tris-(?-N,N'-(4-(2-Thienyl)pyrazolato)trigold(I)) (126):AuCl(tht) (0.320 g, 1.00 mmol) and 118 (0.150 g, 1.00 mmol) were dissolved in 1:1MeOH/-THF. Slow diffusion of triethylamine in 1:1 MeOH/THF over three days afforded colorlessneedles of 126 suitable for SCXRD in 41% yield. m/z: 1038. FT-IR (cm?1), 3111 (w), 2961(w), 1584 (m), 1391 (m), 1358 (m), 1316 (m), 1258 (m), 1217 (m), 1179 (w), 1106 (s), 1076(m), 1052 (m), 1034 (m), 911 (m), 818 (s), 701 (s), 686 (s), 650 (m), 632 (m), 578 (w), 504(m), 454 (m). Elem Calcd for C21H15N6S3Au: C, 24.29; H, 1.46; N, 8.09. Found C, 25.02; H,2.03; N, 7.99.tris-(?-N,N'-(4-(2-Thienyl)3,5-dimethylpyrazolato)trigold(I)) (127):AuCl(tht) (0.320 g, 1.00 mmol) and 119 (0.150 g, 1.00 mmol) were dissolved in 1:1MeOH/-THF. Slow diffusion of triethylamine in 1:1 MeOH/THF over two days afforded a white micro-crystalline powder of 127 in 43 % yield. m/z: 1122. FT-IR (cm?1): 2956 (m) 2908 (m), 2971(m), 1557 (m), 1505 (m), 1430 (s) 1373 (m), 1316 (w), 1258 (m), 1233 (m), 1215 (w), 1156(m), 1120 (w), 1022 (m), 1003 (m), 952 (m), 846 (m), 806 (m), 770 (w), 686 (s), 675 (s), 621(w), 601 (w), 581 (w), 559 (w), 497 (m), 462 (m). Elem Calcd for C27H27N6S3Au3: C, 28.89;H, 2.42; N, 7.49. Found: C, 29.32; H, 2.21; N 7.68.tris-(?-N,N'-(4-[5-(2,2'-Bithienyl)]pyrazolato)trigold(I)) (128):AuCl(tht) (0.320 g, 1.00 mmol) and 120 (0.232 g, 1.00 mmol) were dissolved in 1:1MeOH/-THF. Slow diffusion of triethylamine in 1:1 MeOH/THF over five days afforded gold featheredcrystals of 128 in 39 % yield. m/z: 1284. FT-IR (cm?1): 3108 (w), 2847 (w), 1584 (m), 1539(w), 1463 (w), 1423 (w), 1387 (m), 1346 (m), 1293 (w), 1258 (w), 1173 (m), 1102 (m), 1053(m), 1028 (m), 913 (m), 878 (w), 817 (m), 802 (m), 780 (s), 686 (s), 636 (m), 535 (m), 476(m), 432 (m). Elem Calcd for C33H21N6S6Au3: C, 30.85; H, 1.65; N, 6.54. Found: C, 30.63;H, 1.78; N, 6.30.tris-(?-N,N'-(4-[5-(2,2'-Bithienyl)]3,5-dimethylpyrazolato)trigold(I)) (129):1054.2. ExperimentalAuCl(tht) (0.320 g, 1.00 mmol) and 121 (0.260 g, 1.00 mmol) were dissolved in 1:1MeOH/-THF. Slow diffusion of triethylamine in 1:1 MeOH/THF over one week afforded a yellowpowder of 129 in 36 % yield. m/z: 1368. FT-IR (cm?1): 3066 (w), 2910 (w), 1565 (m), 1532(m), 1490 (w), 1424 (m), 1372 (m), 1308 (w), 1263 (m), 1223 (w), 1199 (w), 1104 (w), 1045(w), 1001 (m), 951 (m), 837 (s), 817 (w), 784 (s), 740 (w), 683 (vs), 634 (w), 581 (m), 478 (s).Elem Calcd for C39H33N6S6Au3: C, 34.22; H, 2.43; N, 6.14. Found: C, 34.36; H, 2.27; N, 5.81.tris-(?-N,N'-(4-[2-(3-Hexylthienyl)]pyrazolato)trigold(I)) (130):AuCl(tht) (0.032 g, 0.10 mmol) and 122 (0.023 g, 0.10 mmol), and triethylamine (14 ?L,0.10 mmol) were dissolved in THF (15 mL) and stirred at room temperature for 20 minutes.The reaction was evaporated to dryness, and the resulting residue was suspended in hexanesand centrifuged. The supernatant was collected, evaporated to dryness, and purified via columnchromatography on silica with 4:1 hexanes:CH2Cl2 as the eluent to give a white solid in 62 %yield. m/z: 1290 (100 %), 2578 (18 %). 1H NMR (400 MHz, CDCl3): ? 7.46 (s, 6H), 7.10 (d,J = 5 Hz, 3H), 6.91 (d, J = 5 Hz, 3H), 2.58 (t, J = 8 Hz, 6H), 1.58 (m, 6H), 1.30 (m, 18H),0.90 (m, 9H). 13C NMR (100 MHz, CDCl3): ? 138.1, 138.0, 129.5, 128.3, 122.2, 115.7, 31.8,30.5, 29.7, 29.1, 22.7, 14.2. FT-IR (cm?1: 2955 (s), 2921 (vs), 2851 (vs), 1580 (w), 1522 (w),1463 (m), 1390 (w), 1361 (w),1338 (w), 1260 (m), 1180 (w), 1084 (s), 1041 (m), 915 (w), 820(m), 802 (s), 730 (w), 691 (w), 647 (m). Elem Calcd for C39H51N6S3Au3: C, 36.29; H, 3.98;N, 6.51. Found: C, 35.99; H, 3.72; N, 6.84.tris-(?-N,N'-(4-[2-(3-Hexylthienyl)]3,5-dimethylpyrazolato)trigold(I)) (131):AuCl(tht) (0.032 g, 0.1 mmol), 123 (0.028 g, 0.11 mmol), and triethylamine (14 ?L,0.10 mmol) were dissolved in THF (5 mL) and stirred at room temperature for one hour. Thereaction mixture was evaporated to dryness, and the resulting residue was dissolved in CH2Cl2(5 mL) and washed with H2O (2 ? 3 mL). The organic layer was dried over MgSO4, filtered,and evaporated to dryness. The crude white solid was purified via column chromatography onsilica with 4:1 hexanes:CH2Cl2 as the eluent to give a white solid in 84 %. Colorless crystals of131 suitable for SCXRD were grown from layering methanol on a CHCl3 solution. m/z: 1347.1H NMR (300 MHz, CDCl3): ? 7.26 (d, J = 5 Hz, 3H), 6.97 (d, J = 5 Hz, 3H), 2.33 (t, J = 8 Hz,6H), 2.08 (s, 18H), 1.44 (m, 6H), 1.19 (m, 18H), 0.84 (m, 9H). 13C NMR (100 MHz, CDCl3):? 147.6, 141.1, 128.7, 128.4, 124.3, 110.4, 31.7, 30.6, 29.7, 29.1, 22.6, 12.5. FT-IR (cm?1):1064.2. Experimental2955 (m), 2922 (vs), 2852 (s), 1580 (w), 1500 (w), 1463 (m), 1375 (m), 1260 (m), 1172 (w),1093 (m, br), 1016 (m), 958 (w), 873 (w), 799 (s), 722 (m), 704 (m), 684 (w), 659 (m), 571(m), 468 (w). Elem Calcd for C45H63N6S3Au3: C, 39.31; H, 4.62; N, 6.11. Found C, 39.50; H,4.12; N, 6.42.tris-(?-N,N'-(4-[5-(3,3'-Dihexyl-2,2'-bithienyl)]pyrazolato)trigold(I)) (132):AuCl(tht) (0.032 g, 0.10 mmol) and 124 (0.040 g, 1 mmol), and triethylamine (14 ?L,0.1 mmol) were dissolved in THF (15 mL) and stirred at room temperature for one hour. The re-action was evaporated to dryness, and the resulting residue was suspended in hexanes (10 mL)and centrifuged. The supernatant was collected, evaporated to dryness, and purified via columnchromatography on silica with 4:1 hexanes:CH2Cl2 as the eluent to give a white solid in 86 %yield. m/z: 1788. 1H NMR (300 MHz, CDCl3): ? 7.51 (s, 6H), 7.28 (d, J = 5 Hz, 3H), 6.97 (d,J = 5 Hz, 3H), 6.88 (s, 3H), 2.56 (t, J = 8 Hz, 6H), 2.46 (t, J = 8 Hz, 6H), 1.54 (m, 12H), 1.25(m, 36H), 0.86 (m, 18H). 13C NMR (100 MHz, CDCl3): ? 136.8, 135.8, 134.6, 128.6, 128.5,128.4, 125.5,125.3, 123.9, 117.0. FT-IR (cm?1: 2955 (s), 2922 (vs), 2854 (s), 1588 (m), 1520(w), 1461 (m), 1399 (w), 1371 (m), 1318 (w), 1262 (s), 1173 (w), 1095 (s), 1041 (vs), 1024(s), 929 (w), 874 (m), 820 (vs), 801 (vs), 719 (m), 694 (w), 642 (m), 567 (m). Elem Calcd forC69H93N6S6Au3: C, 46.30; H, 5.24; N, 4.70. Found C, 46.39; H, 4.91; N, 4.85.tris-(?-N,N'-(4-[5-(3,3'-Dihexyl-2,2'-bithienyl)]3,5-dimethylpyrazolato)trigold(I)) (133):AuCl(tht) (0.032 g, 0.10 mmol) and 125 (0.043 g, 0.11 mmol), and triethylamine (14 ?L,0.1 mmol) were dissolved in THF (15 mL) and stirred at room temperature for one hour. The re-action was evaporated to dryness, and the resulting residue was suspended in hexanes (15 mL)and centrifuged. The supernatant was collected, evaporated to dryness, and purified via col-umn chromatography on silica with 4:1 hexanes:CH2Cl2 as the eluent to give a white solid in87 % yield. m/z: 1872. 1H NMR (300 MHz, CDCl3): ? 7.28 (d, J = 5.4 Hz, 3H), 6.97 (d, J= 5.4 Hz, 3H), 6.76 (s, 3H), 2.56 (t, J = 8.1 Hz, 6H), 2.51 (t, J = 8.1 Hz, 6H), 2.28 (s, 18H),1.54 (m, 12H), 1.25 (m, 36H), 0.86 (m, 18H). 13C NMR (100 MHz, CDCl3): ? 145.5, 142.2,142.1, 136.3, 128.5, 126.3, 125.6, 125.1, 111.7, 31.7, 31.6, 30.8, 30.7, 30.3, 29.2, 29.1, 29.0,28.9, 22.6, 22.5, 14.1, 13.6. FT-IR (cm?1: 2954 (s), 2922 (vs), 2853 (s), 1573 (w), 1546 (m),1501 (m), 1450 (m), 1426 (s), 1374 (s), 1361 (m), 1361 (m), 1198 (w), 1086 (m), 1033 (m),920 (w), 874 (w), 832 (m), 802 (s), 757 (w), 722 (m) 651 (m), 592 (w), 478 (m). Elem Calcdfor C75H105N6S6Au3: C, 48.07; H, 5.65; N, 4.48. Found: C, 48.23; H, 5.31; N: 4.40.1074.3. Results and Discussion4.2.3 X-Ray CrystallographyAll crystals were mounted on glass fibers and were measured on a Bruker APEX DUOdiffractometer with graphite monochromated Mo-K? radiation. Data were collected and inte-grated using the SAINT software package.131 Data were corrected for absorption effects usingthe multiscan technique (SADABS).132 Structures were solved using direct methods.133 Non-hydrogen atoms were refined anisotropically. All non-N?H hydrogens were placed in calcu-lated positions; N?H hydrogens in 118 and 119were found on the difference map. Refinementsfor 118, 119, 126, and 131 were performed using SHELXL-97134 via the WinGX135 interface.Compound 118 crystallizes with disorder about the thiophene ring. Compound 119 crystallizeswith disorder about one of the three independent thiophene rings. Compound 126 crystallizesas a two-component twin and with disorder about one of the thiophene rings. Compound 131crystallizes with disorder in n-hexyl chains. Restraints on bond lengths for the disordered n-hexyl groups were employed to maintain reasonable geometries. Crystallographic details forcompound 118, 119, 126, and 131 can be found in Table A.6. Visualization of the solid statemolecular structures was performed using CrystalMaker?.4.2.4 DFT CalculationsCalculations were performed using density functional theory (DFT) or time dependent den-sity functional theory (TD-DFT) with the B3LYP hybrid functional.210,211 Gold(I) atoms weretreated with the LANL2DZ basis set,212?214 and the 6-31G* basis set215 was employed forall other atoms. Initial calculations were also performed using the CEP-31G(d)216?218 basisset, and qualitatively similar results were obtained. All calculations were performed with theGaussian 09 software package.2194.3 Results and Discussion4.3.1 SynthesisScheme 4.1 and Scheme 4.2 show the synthetic routes for creating the thienyl pyrazoleproligands 118?125, and the molecular structures of these compounds are shown in Chart4.3. Suzuki-Miyaura cross coupling reactions using two different palladium catalysts wereemployed to synthesize proligands 118?125. Use of Pd(PPh3)4 was sufficient for coupling of1084.3. Results and DiscussionS NHN S NN SN NI S S B(OH)2 5% Pd(PPh3)42.2 K2CO33:1 THF:H2OOO OOMeOH/NaOH118 110Scheme 4.1: Synthetic route for proligands 118?121.S NHN S NN O O C(CH3)3NNBOO O C(CH3)3O S Br5% PEPPSI-IPr 2.2 K2CO33:1 THF:H2O MeOH/HCl1 2 2C6H13C6H13 114Scheme 4.2: Synthetic route for proligands 122?125.unsubstituted thiophene derivatives 118?121 to the 4-position of the pyrazole group. Milderconditions were required for syntheses using Boc-protected pyrazoles, otherwise in situ depro-tection of the pyrazole would occur. As a consequence, catalyst PEPPSI-IPr was used for facilesynthesis of protected thienyl pyrazoles.The molecular structures of the thienyl pyrazolate gold(I) complexes are shown in Chart4.4. Synthesis of these complexes is similar to the reaction scheme shown in Scheme 1.6.Compounds 126?129 are insoluble in common organic solvents, and complexes with n-hexylgroups (compounds 130?133) were synthesized to solubilize the molecules so that solutionstate behavior could be studied. This study of coinage metal CTCs was limited to gold(I)1094.3. Results and DiscussionS NHN S NHNS NHN S NHN S NHNS S NHNS S NHNS S NHNS118 119122 123 120124 121125C 6 H13 C 6 H13 C 6 H13C 6 H13 C 6 H13C 6 H13Chart 4.3: Structure of thienyl pyrazole proligands 118?125.N NAuAuN NN Au NR RR R = S S SX XXXXX X = HX = CH3R =X = H   X = CH3R = S S S X = HX = CH3R =X = HX = CH3C6H13 C6H13C6H131 26127 128129130131 13 21 3 3Chart 4.4: Structure of gold(I) cyclic trinuclear complexes 126?133.complexes on account of gold?s atmospheric and photostability.4.3.2 Solid State Molecular StructuresSelected bond lengths and angles for compounds 118, 119, 126, and 131 are listed in Ta-ble A.26?Table A.29. Solid state molecular structures of proligands 118 and 119 are shownin Figure 4.2. Compound 118 crystallizes in the orthorhombic space group P212121 and hasan extended herringbone packing structure. The thiophene ring exists in two orientations, bothof which are coplanar with the pyrazole ring in the solid state (S6A-C4A-C6-C5: -1.0(4)?;S6B-C4B-C6-C7: 178.67(17)?). Information regarding the degree of conjugation can be ob-tained from the C-C bond length between the two aryl groups, though the ring disorder makesthis method of analysis unreliable. Compound 119 crystallizes in the monoclinic space groupC2/c and possesses three crystallographically independent molecules, one of which is disor-dered, that do not pack in any special orientation. The torsion angle between the thiophene and1104.3. Results and Discussiona) b)Figure 4.2: Solid state molecular structures of a) 118; b) 119. Non N?H hydrogens, disorder,and the other independent molecules of 119 have been omitted for clarity. Thermal ellipsoidsare shown at 50 % probability.pyrazole rings are -129.59(16)? (S1-C4-C7-C8), -147.45(15)? (S2-C13-C16-C17), -153.1(11)?(C26-C25-C22-S3), and -151.9(13)? (C24-C25-C22B-S3B).Exposure of proligand 118 and AuCl(tht) to base gives colorless crystals of the nine-membered trimeric species 126 (Figure 4.3). Thienyl pyrazolate torsion angles of the cyclictrinuclear complex are similar with values of -155.4(11)? (C1-C2-C4-S1), -145.4(12)? (C8-C9-C11-S2), -154.4(14)? (C15-C16-C18-S3), and -152(3)? (C17-C16-C18B-S3B). IntramolecularAu?Au distances are typical with values between 3.30 ? and 3.38 ?. Intermolecular Au?Audistances are 3.2170(7) ? (Au1?Au2), 3.5841(7) ? (Au3?Au3), and 3.8049(7) ? (Au2?Au1).Both contacts Au1?Au2 and Au3?Au3 fall within the distance requirement for aurophilic in-teraction.199The thermal ellipsoid on atom C5 is about a third of the size of the other ellipsoids. Thepresence of a small twin component or a disordered orientation of the thiophene ring that couldnot be modeled appropriately may account for the unusual ellipsoid.Figure 4.3b shows that molecules of 126 stack in an ABAB fashion along the c-axis. Therotational angle between the two orientations is approximately 30?, and there are no intermolec-ular ?-? interactions. This rotation angle minimizes repulsive intermolecular interactions fromthe organic linker while maximizing ground state aurophilic interactions. Looking at 126 alongthe c-axis and b-axis (Figure 4.3c) illustrates the interplay of thienyl pyrazolate torsion angleand long range orientation.A preliminary solid state molecular structure of compound 128 was obtained (Figure 4.4).Diffuse scattering and severe twinning due to, in part, the similarity of the b and c axis dimen-1114.3. Results and Discussiona)b) c)Figure 4.3: a) Solid state molecular structure of 126. Hydrogens and disorder have been omit-ted for clarity. Thermal ellipsoids are shown at 50 % probability. Views of two molecules of126 along the b) c-axis; c) b-axis.sions (18.52 ? and 18.70 ?, respectively) prevented a full analysis of the molecular structure.PXRD was used to confirm the preliminary structure by comparing the predicted and experi-mental powder patterns (Figure B.22). Diffraction associated with the 0n0 or 00n reflectionsdominate the powder pattern which may be due to preferred orientation of either the ac or abplane with the plane of the sample holder. The discussion of the structure is limited to the nu-1124.3. Results and DiscussionFigure 4.4: Preliminary solid state molecular structure of 128 viewed along the c-axis.clearity of the molecule as well as the intermolecular proximity of gold atoms and the bridginglinkers to one another. One intermolecular gold(I)?gold(I) contact of 3.216(10) ? is present in128, and the interaction spans to form one dimensional chains of the cyclic trinuclear species.It is notable that the presence of a planar biaryl group at the 4-position of the pyrazolate doesnot prohibit intermolecular aurophilic interactions.The extended structure of compounds 126 and 128 are 1D coordination polymers connectedby noncovalent aurophilic interactions. Molecules of 128 are weakly connected in a staircasestructure, while 126 adopts a rotationally staggered extended structure.Unlike the 1D chains of compounds 126 and 128, molecules of 131 (Figure 4.5a) formdimers in a chair geometry (Figure 4.5b). Gold ions Au1 and Au2 engage in aurophilicinteractions, and the atoms are separated by 3.109(4) ?. Two n-hexyl chains per moleculeare oriented perpendicular to the CTC plane of the molecule, one pointing toward the otherdimer and one pointing away from the dimer, and one chain wraps around and resides adja-cent to the dimeric unit. The orientation of the n-hexyl chains and formation of dimers in thesolid state is similar to that observed in the crystalline phase of tris-(?-N,N'-(3,5-dimethyl-4-octylpyrazolato)trigold(I)) (46, Section 1.3.1).90As seen in the extended structure of 131 in Figure 4.5c, the presence of n-hexyl chainsare a driving force for the formation of isolated dimers rather than 1D polymeric structures.Figure 4.5d shows that there is an intermolecular Au3 ? ? ? S3 contact of 3.290(7) ? whichis less than the sum of the van der Waals radii for these two atoms. Electron density fromthe lone pair on the S3 may interact with an unoccupied orbital on Au3. Near-perpendicularthienyl pyrazolate torsion angles of -84(2)? (C2-C3-C6-S1), 90.4(19)? (C17-C18-C21-S2), and-70(2)? (C32-C33-C36-S3) are attributed to repulsion of the methyl and n-hexyl groups.1134.3. Results and Discussiona) b)c) d)Figure 4.5: a) Solid state molecular structure of 131. Hydrogens and disorder have been omit-ted for clarity. Thermal ellipsoids are shown at 50 % probability. b) Dimer unit of 131. c)Packing of 131. d) Au ? ? ? S contact of two molecules of 131. n-Hexyl chains have beenomitted for clarity.No liquid crystalline behavior was observed with compounds 130?133 that contain n-hexyl derivatives. Gold(I) CTCs with aliphatic groups have demonstrated hexagonal colum-nar mesophases.90,91 Unlike compound 46 where the aliphatic groups are capable of rearrang-ing into a new orientation,90 the orthogonal annular torsion angles of the n-hexyl-thienyl andbithienyl pyrazolates prohibit the planarization of the bridging linkers and subsequent rear-rangement of n-hexyl chains. This planarization was determined to be a requirement for form-1144.3. Results and Discussioning hexagonal columnar mesophases of 46.4.3.3 Electronic Absorption and Emission SpectraA summary of the solution state electron absorption spectra for 118?125 and 130?133 inCH2Cl2 are shown in Table 4.1. Thienyl pyrazole ???? transitions are the primary featuresof the spectra. An increase in conjugation causes bathochromic shifts: the absorption max-ima for the methylated derivatives are higher in energy than the non-methylated counterparts.Coordination of the n-hexyl derivative proligands to gold(I) centers does not cause significanthypsochromic or bathochromic shifts in the absorption maxima.Table 4.1: Solution state absorption data for compounds 118?125 and 130?133 in CH2Cl2 at298 K.Compound ?max (nm) Compound ?max (nm)118 313, 270, 245 119 264, 247120 345, 324, 248 121 340, 245122 305, 255 130 305, 235123 245 131 245, 230124 294, 245 132 305, 255, 235125 285, 245 133 300, 250, 230The photoluminescence spectra of proligands 118?125 show broad or weakly structuredsinglet emission at room temperature in both solution and in the solid state. Upon cooling,the emission features become more structured owing to vibronic coupling within the pyrazoleand thiophene moieties.82,220 No evidence for triplet phosphorescence is present at room tem-perature or 77 K. Phosphorescence has been observed in functionalized terthiophenes at 80 Kwith laser excitation and gated detection221 as well as in thin films of poly(3-hexylthiophene)at 18 K using typical detection methods.222 However, phosphorescence of conjugated bi- andtriaryl thiophenes is often difficult to observe due to slow rates for intersystem crossing andnon-radiative decay pathways that are accessible even at 77 K.221,223,224The variable temperature photoluminescence spectra of complexes 126 and 127 are shownin Figure 4.6. Broad emission features centered at 445 nm and 425 nm, respectively, are presentat room temperature when 126 and 127 are excited at 375 nm. These emission features aresimilar to proligands 118 and 119 and are assigned to a singlet ligand-based transition. Uponcooling, the fine structure of the singlet ligand-based emission becomes apparent. Emissionintensity increases for 126 and remains the same for 127.1154.3. Results and DiscussionTable 4.2: Emission data for proligands 118?125.Compound ?em (nm) Compound ?em (nm)118a 337, 388, 420, 440 119a 338, 415, 430120a 419, 448, 490, 523 121a 418, 440, 482, 512122b 390 123b 380124b 405 125b 400aSolid state. bSolution state, toluene.Table 4.3: Emission data for gold(I) complexes 126?133Compound ?em (nm), 298 K ?em (nm), 77 K126 455 439, 468, 500, 530, 570127 428 399, 424, 453, 509, 536128 440, 505, 534 420, 451, 476, 505, 540129 432, 460, 490, 528 410, 433, 462, 492, 528130a 423 416, 484, 508130b 380 490, 515, 555131a 420 418, 472, 497131b 350, 365 370, 470, 505132a 437, 486 420, 441, 470, 552, 593132b 410, 483415, 438, 469, 496,545, 588133a 418 403, 421, 444133b 403 400, 431aSolid state. bSolution state, toluene.Excitation of 126 and 127 at 315 nm and 298 K shows no emission features. Broad, weaklystructured emission with a lifetime of 2 ms (at 77 K) and centered at 540 nm at 520 nm,respectively, grows in upon cooling. The Stokes shifts of the low temperature phosphores-cence features are 12,000?13,000 cm?1 and are slightly less than reported Stokes shifts ofmetallophilic T1 ? S0 transitions for other cyclic trinuclear complexes.82,93 The magnitudeof the Stokes shifts suggests some geometric distortion occurs between the triplet and singletstates. Two primary geometric changes to consider are contractions of inter- and intramolecu-lar metal-metal distances92,93 and a planarization of the aryl groups.221,223 Structured featuresspaced 1400?1500 cm?1 apart are typical for pyrazolate and thiophene vibronic coupling.220Multiple overlapping unstructured bands that grow in and decay at different rates can causeapparent vibronic structure.82 However, computational modeling supports the assignment of1164.3. Results and Discussionmetal-perturbed ligand-based phosphorescence (vide infra). The long lifetime and Stokes shiftis typical for metal-perturbed ligand-centered phosphorescence from this class of compounds.For example, Omary and co-workers reported structured phenyl-pyrazolate emission featuressensitized by a copper(I) ion in [3-(CF3),5-(Ph)PzCu]3 (47c): a lifetime of 5 ms and Stokesshift of 11,600 cm?1 at 77 K was observed for 47c.82Compounds 130 and 131 exhibit similar variable temperature photoluminescent behaviorto compounds 126 and 127 in solution and in the solid state. A detailed study of compound131 was conducted because of its known solid state molecular structure. At room temperature,structured solution state fluorescence is centered at 360 nm, and weakly structured and broademission is centered at 415 nm in the solid state. Structured luminescence centered at 505 nmand Stokes shift of 11,950 cm?1 grows in gradually in the solid state (Figure 4.7a) and appearssuddenly near the glass transition temperature in toluene (Figure 4.7b). The appearance oflower energy luminescence only upon transitioning to a glassy or solid solution suggests theremay be specific structural requirements such as dimer formation or reduced rotational freedomin addition to reduced non-radiative decay pathways for this radiative process to occur.Unlike monothienyl pyrazolate gold(I) cyclic trinuclear complexes 126?127 and 130?131,singlet emission features dominant the variable temperature photoluminescence spectra ofbithienyl complexes 128 and 129. Inspection of the photoluminescence spectra of 128 and129 in Figure 4.8 and list of ?max in Table 4.2 and Table 4.3 show that the emission profiles arered-shift compared to proligands 120 and 121, featured at room temperature, and the spectrabecome slightly more resolved when cooled. No new emission features develop upon coolingto cryogenic temperatures. For both 128 and 129, excitation between 300 nm and 400 nmproduce emission spectra that are of similar shape and intensity.The photoluminescence spectra of n-hexyl bithienyl compounds 132 and 133 are blue-shifted compared to 128 and 129 and have fewer structured features. The emission spectraof compound 132 in the solid state at 298 K and 77 K are shown in Figure 4.9a. Excitationat 335 nm and 370 nm results in a broad emission feature at 430 nm that shows structureat 77 K. In addition, new features centered at 585 nm appear when the material is cooled.These features are similar in structure and energy to the ligand-based phosphorescence of themonothienyl derivatives. However, monitoring emission at 585 nm shows the excitation fea-ture is broad and centered at 400 nm and the apparent Stokes shift is much smaller with a valueof 7,000 cm?1. The lifetime associated with this transition could not be determined due to thelow emission intensity and overlap of the strong singlet feature. The solution state excitationand emission spectra at 77 K in Figure 4.9b are similar to that in the solid state. Monitoringemission at 550 nm shows multiple low energy features in the excitation spectrum with a max-1174.3. Results and Discussion3 5 0 4 0 0 4 5 0 5 0 0 5 5 002 0 0 0 04 0 0 0 06 0 0 0 08 0 0 0 0Wavelength (nm)Emission(Countss?1 )77 K100 K125 K150 K175 K200 K245 K298 Ka)Wavelength (nm)Emission(Countss?1 )77 K, ?ex = 375 nm298 K, ?ex = 375 nm77 K, ?ex = 315 nm298 K, ?ex = 315 nmb)Figure 4.6: Variable temperature solid state photoluminescence spectra of compounds 126 and127. a) Emission spectra of 126 at ?ex = 375 nm (solid line) and ?ex = 315 nm (dotted line).b) Emission spectra of 127 at 298 K and 77 K.imum of 380 nm. Again, emission lifetime for the low energy feature could not be determined.Inspection of compound 133 in both solution and in the solid state shows emission features1184.3. Results and Discussion350 400 450 500 5500100002000030000Wavelength (nm)Emission(Countss?1 )80 K100 K130 K160 K195 K230 K260 K298 Ka)350 400 450 500 550050000100000150000200000Wavelength (nm)Emission(Countss?1 )80 K100 K125 K150 K175 K200 K255 K298 Kb)Figure 4.7: Variable temperature photoluminescence spectra of compound 131 in a) the solidstate; b) solution. ?ex = 315 nm.centered at 420 nm. No other emission features are apparent when the material is cooled to77 K.Phosphorescence is not observed in unsubstituted bithienyl pyrazolate compounds, and1194.3. Results and Discussion400 450 500 550 6000100000200000300000400000500000600000Wavelength (nm)Emission(Countss?1 )77 K, 128298 K, 12877 K, 129298 K, 129Figure 4.8: Variable temperature solid state photoluminescence spectra of compounds 128 and129.a weak transition appears in 132 that can be associated with ligand-based phosphorescence,oxidized or dissociated ligand or enhancement of singlet excited states at low temperature.Spin-orbit coupling of gold(I) within the S1 state of monothienyl metal complexes enhancesintersystem crossing from the S1 to Tn or T1 state through an ?internal? heavy metal effect.200Computational methods were used to confirm this assignment.4.3.4 DFT CalculationsIn light of the observed photoluminescence spectra as well as the lack of crystallographicdata for most compounds, a preliminary computational study was conducted to support the as-signment of metal-perturbed ligand-based phosphorescence for monothienyl metal complexesand to provide insight for molecular structures. Table 4.4 summarizes annular torsion angles forthe optimized singlet ground state of linkers 118?125. As expected, compounds with methylgroups on the pyrazole have less planar thienyl pyrazole torsion angles. These data confirmwhat was observed in the solid state molecular structure of metal complex 131. Repulsive in-teractions of aliphatic groups in proligands 123?125 cause twisting of the aryl moieties, andthe torsion angles in these compounds are nearly orthogonal.Solid state molecular structures of monothienyl pyrazolate gold(I) cyclic trinuclear com-1204.3. Results and Discussion300 350 400 450 500 550 600020000400006000080000100000120000140000160000Wavelength (nm)Emission(Countss?1 )?ex = 335 nm?ex = 370 nm?ex = 400 nm?em = 430 nm?em = 490 nm?em = 585 nma)300 400 500 600050001000015000200002500030000Wavelength (nm)Emission(Countss?1 )?ex = 365 nm?ex = 380 nm?ex = 405 nm?em = 410 nm?em = 550 nmb)Figure 4.9: Excitation (dashed lines) and emission (solid lines) spectra of compound 132 at77 K. a) Solid state photoluminescence spectra. b) Frozen solution state photoluminescencespectra, in toluene.plexes 126 and 131 were used to calculate the ground state molecular orbitals for these com-pounds. Two key differences between these compounds are the thienyl pyrazolate torsion angle1214.3. Results and DiscussionTable 4.4: Calculated thienyl pyrazole (T-Pz) and thienyl thienyl (T-T) torsion angles of linkers118?125.Compound T-Pz (?) Compound T-Pz (?) T-T (?)118 4.0 120 27.6 158.0119 40.3 121 42.8 157.7122 41.3 124 20.5 104.4123 104.9 125 36.5 104.0Table 4.5: Energies (eV) of frontier orbitals of 126 and 131 in the singlet state.CompoundMonomerHOMOMonomerLUMODimerHOMODimerLUMO126 -5.80 -0.97 -5.67 -1.10131 -5.86 -0.57 -5.73 -0.48of the bridging ligand and, for the dimeric species, the intermolecular orientation of the goldatoms. Frontier orbitals for the monomeric and dimeric species of 126 and 131 in the singletstate are shown in Figure 4.10 and Figure 4.11, respectively.The HOMOs of the monomers and dimers are delocalized along the bridging linkers and areall of similar energy with the dimers being slightly higher in energy (Table 4.5). The LUMO ofthe monomer of 126 is delocalized over the ligands, and the LUMO of the dimer has a mixedmetal-ligand character that includes aurophilic contributions and is lower in energy than themonomer LUMO. Both the monomer and dimer of 131 are calculated to have mostly metalcharacter on the LUMOs rather than mixed metal-ligand orbitals.The partial solid state molecular structure of 128 and the optimized geometry of proligand120 were used to elucidate the electronic structure of the bithienyl complex 128. The goalwas not to determine the precise or optimized structure of these compounds but to confirmthat metal contributions to the frontier orbitals are minimal for this class of compounds andthat metal-perturbed ligand-based phosphorescence as a radiative pathway is not supported.Frontier orbitals of the monomer and dimer of 128 in the S0 state are shown in Figure 4.12. Forthe monomer and dimer, the HOMO is a delocalized ? system and the LUMO is a delocalized?? system with no metal contributions. Orbitals with metal character are found in the LUMO+3and LUMO+6 for the monomer and dimer, respectively.These calculations support the assignment of metal-perturbed ligand-based phosphores-cence rather than the presence of an MLCT or multiple metal-based triplet emitting states.1224.3. Results and Discussiona) b)c) d)Figure 4.10: Molecular orbital contours for 126 in the singlet state. a) Monomer HOMO. b)Monomer LUMO. c) Dimer HOMO. d) Dimer LUMO.For example, a study of a series of 2-pyridyl pyrrolide/phosphine complexes containing d10coinage metal ions found compounds with MLCT character in the LUMO of the S1 state hadenhanced intersystem crossing rates.200 This effect was larger compared to the influence of theatomic number of ?external? heavy metal ion or systems with MLCT character in higher ordersinglet excited states. Systems with metal character in the LUMO of the singlet state, such asmonothienyl pyrazolate gold(I) CTCs, should exhibit intense ligand phosphorescence, while1234.3. Results and Discussiona) b)c) d)Figure 4.11: Molecular orbital contours for the singlet state of monomer and dimeric unit of130. a) Monomer HOMO. b) Monomer LUMO. c) Dimer HOMO. d) Dimer LUMO.the bithienyl analogs will have very weak or no phosphorescence intensity.Attempts at optimizing the triplet excited state geometry for all gold(I) thienyl pyrazo-late CTCs using TD-DFT gave non-converging solutions. Both experimental92 and computa-tional93 studies of CTCs confirm that within a dimeric pair, large intermolecular metal-metalcontractions occur within the triplet excited state geometry because of Tn metallophilic inter-actions. Representative frontier orbitals for the T1 state of 126 are shown in Figure 4.13. Theintermolecular distance of two molecules of compound 126 was adjusted to simulate excitedstate contraction. Vertical contraction of up to 0.5 ? did not cause any significant changesof the ligand ??-based SOMO (singly occupied molecular orbital) or the energy of the mixed1244.3. Results and Discussiona) b)c) d)Figure 4.12: Molecular orbital contours for the singlet state of monomer and dimeric unit of128 using X-ray geometry. a) Monomer HOMO. b) Monomer LUMO. c) Dimer HOMO. d)Dimer LUMO.aurophilic-ligand LUMO or LUMO+1. This trend was also observed with the structure from131 with the n-hexyl chains removed. For all complexes in the T1 state, the ligand-basedSOMO lies well below (at least 1.3 eV) any states with aurophilic contributions. In addition,the energies and contours of the frontier orbitals of the proligands match the gold(I) complexes1254.3. Results and Discussionin both the singlet and triplet states. Achieving a metal-based SOMO in the T1 state wouldrequire an aurophilic state much lower in energy or modification to the electronic structure ofthe bridging linker to increase its triplet energy.a) b)c) d)Figure 4.13: Molecular orbital contours for the triplet state of monomer and dimeric unit of126 using X-ray geometry. a) Monomer HOMO. b) Monomer LUMO. c) Dimer HOMO. d)Dimer LUMO.The annular torsion angle between thienyl and pyrazolate groups was modified to modelplanarization of the bridging linkers in the excited state.221,223 Changing the thienyl pyrazolate1264.3. Results and Discussiontorsion angle from that found in the solid state molecular structure of 126 to 10? decreasedthe energy of the SOMO slightly but did not influence the energy level of the orbitals withaurophilic contributions. Similarly, altering the torsion angle of the bridging linker with twomolecules in the chair position (as in the solid state structure of compound 131) within therange of 90? to 30? caused at most a 0.3 eV change in the energy of the LUMO or SOMO. Thismodel suggests that these changes in ligand geometry do not make a SOMO with aurophiliccontributions accessible.4.3.5 Cyclic Voltammetry and ElectropolymerizationElectropolymerization of oligothiophene complexes can give conductive materials withlonger conjugation path lengths.225 Compounds with solubilizing n-hexyl chains were synthe-sized specifically to investigate the solution state electrochemical properties of gold(I) thienylpyrazolates. The calculated structures of n-hexyl proligands 122?125 and the solid state molec-ular structure of compound 131 suggest that the proligands and bridging linkers of metal com-plexes 130?131 are not planar, and the metal complexes may not be suitable candidates forelectropolymerization. Nonetheless, films of 130, 132, and 133 were grown via oxidative elec-tropolymerization.Table 4.6 summarizes the electrochemical data obtain for compounds 122?125 and 130?133. In general, the reported redox potentials reflect the degree of conjugation within thesecompounds. Molecules with methylated pyrazoles have higher redox potentials compared tothe non-methylated analogs, and bithienyl compounds have lower oxidation potentials than themonothienyl counterparts.Cyclic voltammograms of compounds 122 and 124 are shown in Figure 4.14 and havesimilar features as the methylated counterparts compounds 123 and 125. Compounds 122 and123 both have irreversible oxidations at 1.35 V and 1.46 V, respectively. No new features growin with successive scans suggesting oxidative coupling of the proligand to form a bithienyl bis-pyrazole species does not occur. The initial oxidation of 124 and 125 show two quasi-reversibleredox couples with maximum anodic peaks at 1.05 V and 1.42 V for both compounds. Anoxidative peak at 0.85 V grows in after the first cycle and a small increase in current densityoccurs with successive scans. This behavior indicates the formation of a more conjugatedquarterthienyl bis-pyrazole species (Scheme 4.3). Deposition of oligomers or polymers on thereference electrode was not observed, and oxidative coupling is limited to the formation of adimeric species. Anodic scans past 1.5 V cause over-oxidation and a dropoff in the currentdensity of bithienyl molecules, whereas monothienyl proligands are stable.1274.3. Results and DiscussionTable 4.6: Electrochemical data of compounds 122?125 and 130?133 vs. SCE (saturatedcalomel electrode). Data were collected at a scan rate of 100 mV s?1 in CH2Cl2 with 0.1 M[n-Bu4N][PF6] as the supporting electrolyte.Compound Epa (V) Epc (V)122 1.35, 2.10 2.03123 1.46 1.41, 2.02124 0.86,b 1.05, 1.42 0.85, 1.18125 0.85,b 1.05, 1.42 0.82, 0.96, 1.25130 1.06,b 1.25,a 1.75 0.44, 0.851311.53a; 1.14,b 1.65,1.961.01a,1.25a, 0.59132 0.90,b 1.05 0.77, 0.92133 0.90,b 1.05 0.69, 0.86aFirst scan. bNot present on first scan.-0.5 0 0.5 1 1.5 2-505101520Applied Potential (V vs. SCE)Current(?A)122124Figure 4.14: Cyclic voltammograms of 122 (blue) and 124 (red) on glassy carbon electrode.Starting potentials of 0.21 V and 0.22 V vs. SCE, respectively, were used. Data were col-lected starting in the anodic direction at a scan rate of 100 mV s?1 in CH2Cl2 with 0.1 M[n-Bu4N][PF6] as the supporting electrolyte.1284.3. Results and DiscussionS SC6H13-2H+ SS C6H13S SC6H13 SS C6H13HHNHNNHN C6H13 C6H13S SC6H13 SS C6H13 NHNNHN C6H13 C6H13 NHNNHN C6H13C6H13SSC6H13NHN C6H13 -2e-2Scheme 4.3: Oxidative coupling of proligand to form a a quarterthienyl bis-pyrazole species.Cyclic voltammograms of monothienyl complexes 130 and 131 are shown in Figure 4.15and Figure 4.16, respectively, and do not reflect the behavior of proligands 122 and 123. Oxida-tive scans of compound 130 beyond 1.25 V generate a new anodic peak at 1.06 V that signifiesthe formation of species with a longer conjugation length, presumably oxidatively coupledunits of 130. An anodic shift of the peak centered at 1.75 V occurs with successive cycles andsuggests the material becomes less conjugated with increasing scans. A yellow film depositson the ITO working electrode with successive cycles. Oxidation beyond 2.2 V causes a de-crease in the current intensity and a change in film color from yellow to purple. This behavioris assigned to the irreversible oxidation of the polymer.100Compound 131 exhibits similar electrochemical behavior to 130 during initial voltammetrycycles including the appearance of an oxidative wave at 1.14 V after the first cycle (black trace).The current increases with successive scans (brown and purple traces), and shifts of both anodicand cathodic waves occur (purple, blue, and green traces). A decrease in the current, furthershifts of redox waves, and the formation of a purple residue on the ITO working electrodesuggests irreversible oxidation or decomposition of the material transpired.101Gold(I) complexes 132 and 133 have similar cyclic voltammograms as shown in Fig-ure 4.17 and Figure 4.18. Two oxidative waves are present at 0.90 V and 1.05 V for bothcompounds. Both peaks increase in current intensity with repeated scans which indicates elec-tropolymerization occurred. The peak at 0.90 V, which is not present during the first scan cycle,increases at a faster rate than the peak at 1.05 V. The wave at 0.90 V is attributed to an oxida-tively coupled metal complex species. Successive scans with ITO as the working electroderesults in the deposition of yellow films that turn blue when oxidized. The electrochemical1294.3. Results and Discussion0 0.5 1 1.5 2-50050100150Applied Potential (V vs. SCE)Current(?A)Increasing scansFigure 4.15: Successive cyclic voltammograms of 130 on ITO. A starting potential of 0.26 Vvs. SCE was used. Data were collected starting in the anodic direction at a scan rate of 100mV s?1 in CH2Cl2 with 0.1 M [n-Bu4N][PF6] as the supporting electrolyte.properties of poly-132 and poly-133 are comparable to other gold(I) bithienyl compounds suchas compound 103.204X-ray photoelectron spectroscopy (XPS) was performed on ITO working electrodes aftersuccessive cyclic voltammetry scans of compounds 130?133. Selected elemental compositionsand ratios are shown in Table 4.7. No evidence for other oxidation states of gold besides gold(I)are present. As the cyclic voltammogram of compound 131 suggests, an electropolymerizedfilm is not deposited on ITO. For monothienyl compound 130 and bithienyl compounds 132and 133, the Au:S and Au:N elemental composition ratios are close to the monomer formulaunit of 1:1 and 1:2, respectively.The variable temperature photoluminescence of polymers of 132 and 133 were investi-gated. The photoluminescence spectra of yellow thin films of poly-132 and poly-133 in theirundoped state is shown in Figure 4.19. Polymers were grown by oxidative coupling on ITO-coated quartz substrates. The spectrum at 298 K and 77 K are identical with no significantenhancement in emission intensity or appearance of new features at 77 K. Compared to themonomer in the solid state, the emission maximum is red-shifted and single-featured. Theemission at 500 nm is attributed to a singlet ligand-based electronic transition. An increased1304.3. Results and Discussion-1 -0.5 0 0.5 1 1.5 2-100-50050100150Applied Potential (V vs. SCE)Current(?A)Increasing scansFigure 4.16: Successive cyclic voltammograms of 131 on ITO. A starting potential of 0.21 Vvs. SCE was used. Data were collected starting in the anodic direction at a scan rate of 100mV s?1 in CH2Cl2 with 0.1 M [n-Bu4N][PF6] as the supporting electrolyte.Table 4.7: X-ray photoelectron spectroscopy data for material deposited on ITO after succes-sive voltammetry cycles of 130?133.Compound % Au % S % N Au:S Au:Npoly-(130) 3.65 3.86 4.38 1:1.20 1:1.05poly-(131) 0.13 4.29 6.14 1:36 1:52poly-(132) 3.52 5.36 5.91 1:1.52 1:1.68poly-(133) 3.36 4.81 5.82 1:1.43 1:1.73conjugation length of the bridging linker unit would cause the bathochromic shift in ligand-based emission. While care was taken not to over-oxidize the films, a shoulder at 610 nm ispresent in poly-133 that suggests over-oxidized proligand or polymer may be present in thefilm.1314.4. Conclusions-0.2 0 0.2 0.4 0.6 0.8 1 1.2 1.4-10-505Applied Potential (V vs. SCE)Current(?A)Increasing scansFigure 4.17: Cyclic voltammogram of 132 on ITO. A starting potential of 0.22 V vs. SCE wasused. Data were collected starting in the anodic direction at a scan rate of 50 mV s?1 in CH2Cl2with 0.1 M [n-Bu4N][PF6] as the supporting electrolyte.4.4 ConclusionsPhotoluminescent gold(I) cyclic trinuclear complexes containing thienyl pyrazolate bridg-ing linkers were synthesized and characterized. The presence of aryl, biaryl, or alkylated arylgroups at the 4-position of the pyrazolate does not prohibit the formation of dimeric speciesin the solid state. The orientation of n-hexyl groups prevented the formation of a polymericspecies in 131 as a consequence of the thienyl pyrazolate torsion angle. All metal complexesemit ligand-based fluorescence that is similar to proligand emission. For monothienyl com-plexes, phosphorescence is observed when samples are cooled. Computational studied showedthat phosphorescence is sensitized from aurophilic contributions to the singlet LUMO. Facilita-tion of intersystem crossing to a metal-perturbed ligand-based state does not occur in bithienylcomplexes due to low lying ligand excited state contributions. Oligomeric or polymeric thinfilms of gold(I) thienyl pyrazolates have been synthesized from soluble precursors, and thepresence of gold(I) in the films was confirmed by X-ray photoelectron spectroscopy. The red-shifted singlet emission from these films is assigned to fluorescence from oxidatively coupledlinkers.1324.4. Conclusions-0 .5 0 0.5 1-15-10-5051015Applied Potential (V vs. SCE)Current(?A)Increasing scansFigure 4.18: Cyclic voltammogram of 133 on ITO. A starting potential of 0.23 V vs. SCEwas used. Data were collected starting in the anodic direction at a scan rate of 100 mV s?1 inCH2Cl2 with 0.1 M [n-Bu4N][PF6] as the supporting electrolyte.300 350 400 450 500 550 600020000400006000080000100000120000140000Wavelength (nm)Emission(Countss?1 )?em = 520 nm, poly-132?em = 495 nm, poly-133?ex = 365 nm, poly-132?ex = 400 nm, poly-133Figure 4.19: Excitation (dashed) and emission (solid) spectra of polymers of 132 and 133.133Chapter 5Summary and Future Work5.1 SummaryAs stated in Section 1.5, this thesis investigated the orientational and structural controlof oligothiophene solid state coordination polymers and cyclic trinuclear complexes and es-tablished relationships between the structure and function of these materials. Oligothiophenedicarboxylic acids, including those with phenyl and n-hexyl moieties, were reacted with firstrow transition metals to produce a diverse series of coordination polymers. Gold(I) thienylpyrazolate cyclic trinuclear complexes are capable of engaging in intermolecular aurophilicinteractions to form dimeric and polymeric species. Photoluminescent and magnetic propertiescorrelate to both the local and extended structures of these compounds.Solvothermal and room temperature reaction conditions were employed to synthesize pho-toluminescent zinc(II) bi- and terthienyl coordination polymers. Mixed H2T2DC and N-hetero-cyclic linker (4,4'-bpy and bpe) zinc(II) coordination polymers 76 and 79 are interpenetratedand isostructural 3D frameworks. Solvothermal reactions with functionalized bithienyl linkersH23PhT2DC (67) and H23HT2DC (68) with N-heterocyclic linkers gave 2D sheets of frame-works 74 and 75 which do not include linkers 4,4'-bpy or bpe. Milder synthetic conditionswere required to form mixed linker coordination polymers 77, 78, 80, and 81, none of whichare isostructural. Bithienyl coordination polymers adopt a range of annular torsion angles thatdo not correspond to the energetic minimum of the unbound linker. The orientation of theoligothiophene linker directs the extended structure of coordination polymers.The photoluminescent properties of most zinc(II) coordination polymers reflected those ofthe bridging oligothiophene linker. A hypsochromic shift was observed between proligand68 and 75, while a bathochromic shift occurs between H2T3DC (63) and 83. Quenching ofemission from 68 as a consequence of an incomplete energy transfer to linker bpe occurs in 81.The solid state molecular structures and magnetic susceptibility of non-luminescent bithio-phene and terthiophene coordination polymers were discussed in Chapter 3. The evaluatedcompounds all demonstrated antiferromagnetic behavior typical of manganese(II) coordina-tion polymers. The variable temperature magnetic susceptibility of 94 and 98 reflect the linear1345.1. Summarytrinuclear and binuclear metal centers, respectively, while the behavior of 92 was sufficientlydescribed using the Fischer infinite chain model in conjunction with paramagnetic treatmentof the mononuclear centers. Compound 96 behaves as an antiferromagnet between 300 K and60 K and undergoes a transition at TC = 40 K to a magnetically ordered canted state. Below20 K, antiferromagnetic interactions dominate compound 96.The structural trends of coordination polymers containing beta-substituted oligothiophenesdemonstrates how appropriately chosen functional groups can influence the extended structureof coordination polymers. Diphenyl bithiophene coordination polymers form 2D sheets (74,80, 92, 93) or coordination networks (77). Hydrophobic pockets of n-hexyl chains were foundin the solid state structures of 3D coordination polymers 81 and 94, and PXRD patterns of bothcompounds show that the structural integrity of both compounds is sensitive to desolvation.Compounds 85 and 96?98 are the first crystallographically characterized terthiophene coordi-nation polymers. Compounds 96 and 97 are isomers and are distinguishable by color and IRspectrum in addition to solid state molecular structure.Chapter 4 examined the structure and photoluminescence of mono- and bithienyl pyrazoles(118?125) and cyclic trinuclear complexes (CTCs) of gold(I) thienyl pyrazolates (126?133).Solid state molecular structures of 126, 128, and 131 indicate that aryl and biaryl groups atthe 4-position of CTCs do not obstruct the formation of coordination polymers via aurophilicinteractions. At room temperature, all complexes emit short lived fluorescence that is similarto the constituent proligand. Phosphorescence lifetimes of 5 ms were measured for gold(I)monothienyl pyrazolates at 77 K, while singlet emission was observed for bithienyl species.Computational analyses of dimeric species of 126 and 131 suggest the singlet state LUMO hasintermolecular aurophilic contributions that sensitize intersystem crossing to a ligand-basedtriplet state. Modeling changes in intermolecular gold(I)-gold(I) distances and thienyl pyrazo-late torsion angles did not produce significant changes in the triplet energies of dimers of 126or 131. n-Hexyl groups were appended to thienyl moieties to solubilize the gold(I) complexes.Electrochemical oxidative coupling of 130, 132, and 133 generated conductive luminescentthin films while 131 degraded. The luminescence of the thin films is red shifted from themonomers and originates from oxidatively coupled linkers.Overall, these results show that the extended structure and properties of coordination poly-mers can be tuned by the local structure of the organic linker. The extended structure andorientation within mixed linker systems influence photoluminescent properties, and magneticsusceptibility measurements mirror the local and extended structure of coordination polymers.Functional groups on the periphery of bridging linkers, particularly n-hexyl chains, are strongstructure directing agents within coordination polymers. Gold(I) cyclic trinuclear complexes1355.2. Future Workcontaining thienyl pyrazolate bridging linkers are dimeric or coordination polymers in the solidstate through unsupported aurophilic interactions and in the presence of sterically bulky moi-eties. Electrochemical oxidative coupling of the thienyl groups produces conductive thin films.5.2 Future WorkAlthough oligo- and polythiophenes are of interest for potential applications in photo-voltaics and other energy devices, the late transition metals and hard donor properties of car-boxylates used in this thesis would give rise to poor materials for energy storage or chargetransport. Choosing soft, unsaturated metal centers would allow for more facile electronic com-munication throughout the material. Lowering the oxidation potential of the bridging linkerwould make oligothiophene coordination polymers particularly attractive for synthesizing newconductive solid state materials through electrochemical methods.226 Future considerations fordeveloping such materials should take into account how the coordination polymer will connectwith other portions of a device.Seeing that aliphatic chains direct the extended structure of coordination polymers, replac-ing n-hexyl chains with aliphatic groups that can be removed through a post-synthetic modifi-cation has the potential to form robust three-dimensional materials with tunable pore size andhigh surface areas. These pores would make the frameworks accessible to guest analytes, andthe material could be developed to behave as a sensor or for separations. The route taken forpost-synthetic modification would need to not influence the coordination environment or oxida-tion state around the metal center, and the functionality added to the organic linker would needto be stable under solvothermal reaction conditions. Ideally, the post-synthetic modificationwould be thermally or photochemically driven.Adding a carboxylic acid functional group at the ?-position of thienyl pyrazoles presentedin Chapter 4 would produce a suitable ligand class for augmenting the set of oligothiophenecoordination polymers discussed in this thesis (134, Chart 5.1). Thienyl pyrazole carboxylicacids do not have inversion symmetry and are good candidates for developing materials forsecond harmonic generation. Additionally, a thienyl pyrazole carboxylic acid could be usedas a bridging linker in coinage metal cyclic trinuclear complexes (135). The cyclic trinuclearcomplex shown in Chart 5.1 could be reacted with an appropriate precursor to generate mixedmetal coordination polymers. Further work could address the extent that the presence of onen-hexyl chain per organic linker would direct the extended structure of coordination polymers.Tuning the electronic structure of gold(I) thienyl pyrazolate cyclic trinuclear complexes1365.2. Future WorkS NNHHO 2C C6H13134 N NAuAuN NN Au N SSS CO 2HHO 2CHO 2C C6H13C6H13C6H13 135Chart 5.1: Example of thienyl pyrazole carboxylic acid (134); thienyl pyrazole carboxylic acidcyclic trinuclear complex (135). N NAuAuN NN Au N SSS 136Chart 5.2: Structure of 136.could be achieved by modifying the physical and electronic structure of the bridging thienylpyrazole. Raising the triplet energy of the bridging linker in gold(I) thienyl pyrazolate CTCsas well as increasing the temperature at which metal-perturbed ligand-based phosphorescenceoccurs are both required before these molecules could be used as metal-organic light emittingdiodes. Eliminating the path of conjugation between the thienyl and pyrazolate moieties witha methylene bridge (136, Chart 5.2) is one possible route for achieving this goal. Changes inthe extended structure could also be accomplished through incorporating other d10 metals intothe cyclic trinuclear complexes.137Bibliography[1] Satpati, A.; Nath, S.; Kumbhakar, M.; Maity, D.; Senthilkumar, S.; Pal, H. J. Mol. Struct.2008, 878, 84?94.[2] Do?ssel, L. F.; Kamm, V.; Howard, I. A.; Laquai, F.; Pisula, W.; Feng, X.; Li, C.;Takase, M.; Kudernac, T.; De Feyter, S.; Mu?llen, K. J. Am. Chem. Soc. 2012, 134,5876?5886.[3] Ooyama, Y.; Ohshita, J.; Harima, Y. Chem. Lett. 2012, 41, 1384?1396.[4] Bhosale, R.; M??s?ek, J.; Sakai, N.; Matile, S. Chem. Soc. Rev. 2010, 39, 138?149.[5] Chung, I.; Lee, B.; He, J.; Chang, R. P. H.; Kanatzidis, M. G. Nature 2012, 485, 486?489.[6] Ishii, A.; Miyasaka, T. Chem. Commun. 2012, 48, 9900?9902.[7] Chappaz-Gillot, C. et al. J. Am. Chem. Soc. 2012, 134, 944?954.[8] Rybtchinski, B.; Sinks, L. E.; Wasielewski, M. R. J. Am. Chem. Soc. 2004, 126, 12268?12269.[9] Oliva, M. M.; Casado, J.; Hennrich, G.; Lo?pez Navarrete, J. T. J. Phys. Chem. B 2006,110, 19198?19206.[10] Vollmer, M. S.; Wu?rthner, F.; Effenberger, F.; Emele, P.; Meyer, D. U.; Stu?mpfig, T.;Port, H.; Wolf, H. C. Chem. Eur. J. 1998, 4, 260?269.[11] Schuster, D. I.; Cheng, P.; Jarowski, P. D.; Guldi, D. M.; Luo, C.; Echegoyen, L.; Pyo, S.;Holzwarth, A. R.; Braslavsky, S. E.; Williams, R. M.; Klihm, G. J. Am. Chem. Soc. 2004,126, 7257?7270.[12] El-Khouly, M. E.; Ito, O.; Smith, P. M.; D?Souza, F. J. Photochem. Photobiol. C 2004,5, 79?104.[13] Saini, S.; Srinivas, G.; Bagchi, B. J. Phys. Chem. B 2009, 113, 1817?1832.[14] Wasielewski, M. R. Acc. Chem. Res. 2009, 42, 1910?1921.[15] Kitagawa, S.; Kitaura, R.; Noro, S.-i. Angew. Chem. Int. Ed. 2004, 43, 2334?2375.[16] Briehn, C. A.; Kirschbaum, T.; Ba?uerle, P. J. Org. Chem 2000, 65, 352?359.138Bibliography[17] Tanaka, S.; Tamba, S.; Tanaka, D.; Sugie, A.; Mori, A. J. Am. Chem. Soc. 2011, 133,16734?16737.[18] Wu, X.; Chen, T.-A.; Rieke, R. D. Macromolecules 1996, 29, 7671?7677.[19] Guilera, G.; W. Steed, J. Chem. Commun. 1999, 1563?1564.[20] Abbasi, A.; Geranmayeh, S.; Skripkin, M. Y.; Eriksson, L. Dalton Trans. 2012, 41,850?859.[21] Katz, M. J.; Sakai, K.; Leznoff, D. B. Chem. Soc. Rev. 2008, 37, 1884?1895.[22] Zhao, D.; Timmons, D. J.; Yuan, D.; Zhou, H.-C. Acc. Chem. Res. 2011, 44, 123?133.[23] Eddaoudi, M.; Moler, D. B.; Li, H.; Chen, B.; Reineke, T. M.; O?Keeffe, M.;Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319?330.[24] Dunbar, K. R.; Heintz, R. A. Progress in Inorganic Chemistry; John Wiley & Sons, Inc.,2007; pp 283?391.[25] Hoskins, B. F.; Robson, R. J. Am. Chem. Soc. 1990, 112, 1546?1554.[26] Fujita, M.; Yazaki, J.; Ogura, K. J. Am. Chem. Soc. 1990, 112, 5645?5647.[27] Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem. Soc. 1994, 116, 1151?1152.[28] Kondo, M.; Yoshitomi, T.; Matsuzaka, H.; Kitagawa, S.; Seki, K. Angew. Chem. Int. Ed.1997, 36, 1725?1727.[29] Batten, S. R.; Champness, N. R.; Chen, X.-M.; Garcia-Martinez, J.; Kitagawa, S.;O?hrstro?m, L.; O?Keeffe, M.; Suh, M. P.; Reedijk, J. Pure Appl. Chem. 2013, 85, 1715?1724.[30] Venkataraman, D.; Lee, S.; Moore, J. S.; Zhang, P.; Hirsch, K. A.; Gardner, G. B.;Covey, A. C.; Prentice, C. L. Chem. Mater. 1996, 8, 2030?2040.[31] Larsson, K. Acta Crystallogr., Sect. E 2001, 57, m195?m197.[32] Eddaoudi, M.; Li, H.; Reineke, T.; Fehr, M.; Kelley, D.; Groy, T. L.; Yaghi, O. Top.Catal. 1999, 9, 105?111.[33] Shimizu, G. K. H.; Vaidhyanathan, R.; Taylor, J. M. Chem. Soc. Rev. 2009, 38, 1430?1449.[34] Zhu, A.-X.; Lin, J.-B.; Zhang, J.-P.; Chen, X.-M. Inorg. Chem. 2009, 48, 3882?3889.[35] D?Alessandro, D.; Smit, B.; Long, J. Angew. Chem. Int. Ed. 2010, 49, 6058?6082.139Bibliography[36] Chen, B.; Xiang, S.; Qian, G. Acc. Chem. Res. 2010, 43, 1115?1124.[37] Dhakshinamoorthy, A.; Alvaro, M.; Garcia, H. Chem. Commun. 2012, 48, 11275?11288.[38] Stock, N.; Biswas, S. Chem. Rev. 2012, 112, 933?969.[39] Wang, C.; Zhang, T.; Lin, W. Chem. Rev. 2012, 112, 1084?1104.[40] Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. Chem. Soc. Rev. 2009, 38,1330?1352.[41] Zhang, W.; Xiong, R.-G. Chem. Rev. 2012, 112, 1163?1195.[42] Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; Couvreur, P.; Fe?rey, G.;Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232?1268.[43] Kurmoo, M. Chem. Soc. Rev. 2009, 38, 1353?1379.[44] Batten, S. R. In Metal-Organic Frameworks: Design and Application;MacGillivray, L. R., Ed.; John Wiley & Sons, Inc.: Hoboken, New Jersey, 2010;Chapter Topology and Interpenetration, pp 91?130.[45] Liu, Q.-Y.; Yuan, D.-Q.; Xu, L. Cryst. Growth Des. 2007, 7, 1832?1843.[46] Li, H.; Eddaoudi, M.; O?Keeffe, M.; Yaghi, O. M. Nature 1999, 402, 276?279.[47] Earl, L. D.; Patrick, B. O.; Wolf, M. O. CrystEngComm 2012, 14, 5801?5808.[48] Chun, H.; Jung, H.; Koo, G.; Jeong, H.; Kim, D.-K. Inorg. Chem. 2008, 47, 5355?5359.[49] Alexandrov, E. V.; Blatov, V. A.; Kochetkov, A. V.; Proserpio, D. M. CrystEngComm2011, 13, 3947?3958.[50] Blatov, V. A.; O?Keeffe, M.; Proserpio, D. M. CrystEngComm 2010, 12, 44?48.[51] O?Keeffe, M.; Peskov, M. A.; Ramsden, S. J.; Yaghi, O. M. Acc. Chem. Res. 2008, 41,1782?1789.[52] Cui, Y.; Yue, Y.; Qian, G.; Chen, B. Chem. Rev. 2012, 112, 1126?1162.[53] Li, X.; Wang, X.-W.; Zhang, Y.-H. Inorg. Chem. Commun. 2008, 11, 832?834.[54] Wei, Y.; Yu, Y.; Wu, K. Cryst. Growth Des. 2008, 8, 2087?2089.[55] Whan, R.; Crosby, G. J. Mol. Spectrosc. 1962, 8, 315?327.[56] Chandler, B. D.; Cramb, D. T.; Shimizu, G. K. H. J. Am. Chem. Soc. 2006, 128, 10403?10412.140Bibliography[57] Kent, C. A.; Mehl, B. P.; Ma, L.; Papanikolas, J. M.; Meyer, T. J.; Lin, W. J. Am. Chem.Soc. 2010, 132, 12767?12769.[58] Lee, C. Y.; Farha, O. K.; Hong, B. J.; Sarjeant, A. A.; Nguyen, S. T.; Hupp, J. T. J. Am.Chem. Soc. 2011, 133, 15858?15861.[59] Clapp, A. R.; Medintz, I. L.; Mattoussi, H. ChemPhysChem 2006, 7, 47?57.[60] Toh, N. L.; Nagarathinam, M.; Vittal, J. J. Angew. Chem. Int. Ed. 2005, 44, 2237?2241.[61] Michaelides, A.; Skoulika, S.; Siskos, M. G. Chem. Commun. 2004, 0, 2418?2419.[62] Toda, F. Organic Solid State Reactions; Springer Berlin Heidelberg, 2005; Vol. 254; pp1?40.[63] Liu, Y.; Xu, X.; Zheng, F.; Cui, Y. Angew. Chem. Int. Ed. 2008, 47, 4538?4541.[64] Shoji, I.; Kondo, T.; Kitamoto, A.; Shirane, M.; Ito, R. J. Opt. Soc. Am. B 1997, 14,2268?2294.[65] Evans, O. R.; Xiong, R.-G.; Wang, Z.; Wong, G. K.; Lin, W. Angew. Chem. Int. Ed.1999, 38, 536?538.[66] Evans, O. R.; Wang, Z.; Xiong, R.-G.; Foxman, B. M.; Lin, W. Inorg. Chem. 1999, 38,2969?2973.[67] Evans, O. R.; Lin, W. Chem. Mater. 2001, 13, 2705?2712.[68] Xie, Z.; Ma, L.; deKrafft, K. E.; Jin, A.; Lin, W. J. Am. Chem. Soc. 2010, 132, 922?923.[69] Lan, A.; Li, K.; Wu, H.; Olson, D.; Emge, T.; Ki, W.; Hong, M.; Li, J. Angew. Chem.Int. Ed. 2009, 48, 2334?2338.[70] Miyasaka, H. Acc. Chem. Res. 2013, 46, 248?257.[71] Alvaro, M.; Carbonell, E.; Ferrer, B.; Llabre?s i Xamena, F.; Garcia, H. Chem. Eur. J.2007, 13, 5106?5112.[72] Narayan, T. C.; Miyakai, T.; Seki, S.; Dinca?, M. J. Am. Chem. Soc. 2012, 134, 12932?12935.[73] Motokawa, N.; Matsunaga, S.; Takaishi, S.; Miyasaka, H.; Yamashita, M.; Dunbar, K. R.J. Am. Chem. Soc. 2010, 132, 11943?11951.[74] Pinkowicz, D.; Podgajny, R.; Gawe?, B.; Nitek, W.; ?asocha, W.; Oszajca, M.;Czapla, M.; Makarewicz, M.; Ba?anda, M.; Sieklucka, B. Angew. Chem. Int. Ed. 2011,50, 3973?3977.[75] Coronado, E.; Minguez Espallargas, G. Chem. Soc. Rev. 2013, 42, 1525?1539.141Bibliography[76] Ohba, M.; Yoneda, K.; Agust??, G.; Mun?oz, M.; Gaspar, A.; Real, J.; Yamasaki, M.;Ando, H.; Nakao, Y.; Sakaki, S.; Kitagawa, S. Angew. Chem. Int. Ed. 2009, 48, 4767?4771.[77] Quesada, M.; delaPen?a O?Shea, V.; Arom??, G.; Geremia, S.; Massera, C.; Roubeau, O.;Gamez, P.; Reedijk, J. Adv. Mater. 2007, 19, 1397?1402.[78] Coronado, E.; Gime?nez-Marque?s, M.; M??nguez Espallargas, G. Inorg. Chem. 2012, 51,4403?4410.[79] Burini, A.; Mohamed, A. A.; Fackler, J. P. Comments Inorg. Chem. 2003, 24, 253?280.[80] Mohamed, A. A. Coord. Chem. Rev 2010, 254, 1918?1947.[81] Kishimura, A.; Yamashita, T.; Aida, T. J. Am. Chem. Soc. 2005, 127, 179?183.[82] Dias, H. V. R.; Diyabalanage, H. V. K.; Eldabaja, M. G.; Elbjeirami, O.; Rawashdeh-Omary, M. A.; Omary, M. A. J. Am. Chem. Soc. 2005, 127, 7489?7501.[83] Vaughan, L. G. J. Am. Chem. Soc. 1970, 92, 730?731.[84] Bonati, F.; Burini, A.; Pietroni, B. R.; Bovio, B. J. Organomet. Chem. 1989, 375, 147?160.[85] Yang, G.; Raptis, R. G. Inorg. Chem. 2003, 42, 261?263.[86] Fujisawa, K.; Ishikawa, Y.; Miyashita, Y.; Okamoto, K.-i. Inorg. Chim. Acta 2010, 363,2977?2989.[87] Jozak, T.; Sun, Y.; Schmitt, Y.; Lebedkin, S.; Kappes, M.; Gerhards, M.; Thiel, W. R.Chem. Eur. J. 2011, 17, 3384?3389.[88] He, J.; Yin, Y.-G.; Wu, T.; Li, D.; Huang, X.-C. Chem. Commun. 2006, 0, 2845?2847.[89] Zhang, J.-P.; Kitagawa, S. J. Am. Chem. Soc. 2008, 130, 907?917.[90] Kim, S. J.; Kang, S. H.; Park, K.-M.; Kim, H.; Zin, W.-C.; Choi, M.-G.; Kim, K. Chem.Mater. 1998, 10, 1889?1893.[91] Barbera?, J.; Elduque, A.; Gime?nez, R.; Lahoz, F. J.; Lo?pez, J. A.; Oro, L. A.; Ser-rano, J. L. Inorg. Chem. 1998, 37, 2960?2967.[92] Vorontsov, I. I.; Kovalevsky, A. Y.; Chen, Y.-S.; Graber, T.; Gembicky, M.;Novozhilova, I. V.; Omary, M. A.; Coppens, P. Phys. Rev. Lett. 2005, 94, 193003.[93] Grimes, T.; Omary, M. A.; Dias, H. V. R.; Cundari, T. R. J. Phys. Chem. A 2006, 110,5823?5830.142Bibliography[94] Zhang, J.-X.; He, J.; Yin, Y.-G.; Hu, M.-H.; Li, D.; Huang, X.-C. Inorg. Chem. 2008,47, 3471?3473.[95] Tekarli, S. M.; Cundari, T. R.; Omary, M. A. J. Am. Chem. Soc. 2008, 130, 1669?1675.[96] Goldoni, F.; Antolini, L.; Pourtois, G.; Schenning, A. P. H. J.; Janssen, R. A. J.; Lazza-roni, R.; Bre?das, J.-L.; Meijer, E. W. Eur. J. Inorg. Chem. 2001, 2001, 821?828.[97] Ba?uerle, P. Adv. Mater. 1993, 5, 879?886.[98] Angelici, R. J. Coord. Chem. Rev 1990, 105, 61?76.[99] Ba?uerle, P. In Electronic Materials: The Oligomer Approach; Mu?llen, K., Wegner, G.,Eds.; WILEY-VCH, 1998; Chapter Sulfur-Containing Oligomers: Oligothiophenes, pp105?197.[100] Perepichka, I. F., Perepichka, D. F., Eds. Handbook of Thiophene-Based Materials: Ap-plications in Organic Electronics and Photonics; Wiley: West Sussex, 2009.[101] Krische, B.; Zagorska, M. Synth. Met. 1989, 28, 263?268.[102] Gavezzotti, A.; Filippini, G. Synth. Met. 1991, 40, 257?266.[103] Horowitz, G.; Bachet, B.; Yassar, A.; Lang, P.; Demanze, F.; Fave, J.-L.; Garnier, F.Chem. Mater. 1995, 7, 1337?1341.[104] Marsella, M. J.; Swager, T. M. J. Am. Chem. Soc. 1993, 115, 12214?12215.[105] Iwasaki, K.; Fujimoto, H.; Matsuzaki, S. Synth. Met. 1994, 63, 101?108.[106] Park, Y. D.; Lee, H. S.; Choi, Y. J.; Kwak, D.; Cho, J. H.; Lee, S.; Cho, K. Adv. Funct.Mater. 2009, 19, 1200?1206.[107] DeLongchamp, D. M.; Kline, R. J.; Jung, Y.; Lin, E. K.; Fischer, D. A.; Gundlach, D. J.;Cotts, S. K.; Moad, A. J.; Richter, L. J.; Toney, M. F.; Heeney, M.; McCulloch, I. Macro-molecules 2008, 41, 5709?5715.[108] Wong, W.-Y.; Choi, K.-H.; Lu, G.-L.; Lin, Z. Organometallics 2002, 21, 4475?4481.[109] Chen, F.; Mehta, P. G.; Takiff, L.; McCullough, R. D. J. Mater. Chem. 1996, 6, 1763?1766.[110] Greenham, N.; Samuel, I.; Hayes, G.; Phillips, R.; Kessener, Y.; Moratti, S.; Holmes, A.;Friend, R. Chem. Phys. Lett. 1995, 241, 89?96.[111] Di Ce?sare, N.; Bellete?te, M.; Durocher, G.; Leclerc, M. Chem. Phys. Lett. 1997, 275,533?539.143Bibliography[112] Chen, Q.; Guo, P.-C.; Zhao, S.-P.; Liu, J.-L.; Ren, X.-M. CrystEngComm 2013, 15,1264?1270.[113] Zhan, C.-H.; Wang, F.; Kang, Y.; Zhang, J. Inorg. Chem. 2011, 51, 523?530.[114] Wang, J.-G.; Huang, C.-C.; Huang, X.-H.; Liu, D.-S. Cryst. Growth Des. 2008, 8, 795?798.[115] Marques, L. F.; dos Santos, M. V.; Ribeiro, S. J. L.; Castellano, E. E.; Machado, F. C.Polyhedron 2012, 38, 149?156.[116] Xu, J.; Cheng, J.; Su, W.; Hong, M. Cryst. Growth Des. 2011, 11, 2294?2301.[117] Zhang, Z.; Xiang, S.; Chen, Y.-S.; Ma, S.; Lee, Y.; Phely-Bobin, T.; Chen, B. Inorg.Chem. 2010, 49, 8444?8448.[118] Bon, V.; Senkovska, I.; Baburin, I. A.; Kaskel, S. Cryst. Growth Des. 2013, 13, 1231?1237.[119] Rueff, J.-M.; Perez, O.; Pautrat, A.; Barrier, N.; Hix, G. B.; Hernot, S.; Couthon-Gourve`s, H.; Jaffre`s, P.-A. Inorg. Chem. 2012, 51, 10251?10261.[120] Jia, H.-P.; Li, W.; Ju, Z.-F.; Zhang, J. Eur. J. Inorg. Chem. 2006, 2006, 4264?4270.[121] Kettner, F.; Worch, C.; Moellmer, J.; Gla?ser, R.; Staudt, R.; Krautscheid, H. Inorg.Chem. 2013, 52, 8738?8742.[122] Yaghi, O. M.; Li, H. J. Am. Chem. Soc. 1995, 117, 10401?10402.[123] Bertrand, G. H. V.; Michaelis, V. K.; Ong, T.-C.; Griffin, R. G.; Dinca?, M. PNAS 2013,110, 4923?4928.[124] Zhao, J.; Wang, X.-L.; Shi, X.; Yang, Q.-H.; Li, C. Inorg. Chem. 2011, 50, 3198?3205.[125] Bureekaew, S.; Sato, H.; Matsuda, R.; Kubota, Y.; Hirose, R.; Kim, J.; Kato, K.;Takata, M.; Kitagawa, S. Angew. Chem. Int. Ed. 2010, 49, 7660?7664.[126] Clot, O.; Wolf, M. O.; Patrick, B. O. J. Am. Chem. Soc. 2001, 123, 9963?9973.[127] Ni, Z.; Yassar, A.; Antoun, T.; Yaghi, O. M. J. Am. Chem. Soc. 2005, 127, 12752?12753.[128] Naudin, E?.; El Mehdi, N.; Soucy, C.; Breau, L.; Be?langer, D. Chem. Mater. 2001, 13,634?642.[129] Xia, P. F.; Lu, J.; Kwok, C. H.; Fukutani, H.; Wong, M. S.; Tao, Y. J. Polym. Sci. Pol.Chem. 2009, 47, 137?148.[130] de Bettencourt-Dias, A.; Poloukhtine, A. J. Phys. Chem. B 2006, 110, 25638?25645.144Bibliography[131] SAINT, Version 7.60A. Bruker AXS Inc.: Madison, Wisconsin, USA, 1997-2009.[132] SADABS. Bruker AXS Inc.: Madison, Wisconsin, USA, 2008.[133] Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.; Giacovazzo, C.;Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna, R. J. Appl. Crystallogr. 1999,32, 115?119.[134] Sheldrick, G. M. SHELXL-97, Programs for Crystal Structure Analysis, Release 97-2.Institu?t fu?r Anorganische Chemie der Universita?t Go?ttingen: Go?ttingen, Germany, 1998.[135] Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837?838.[136] van der Sluis, P.; Spek, A. L. Acta Crystallogr., Sect. A 1990, 46, 194?201.[137] Burrows, A. D.; Cassar, K.; Friend, R. M. W.; Mahon, M. F.; Rigby, S. P.; Warren, J. E.CrystEngComm 2005, 7, 548?550.[138] Hawxwell, S. M.; Brammer, L. CrystEngComm 2006, 8, 473?476.[139] Senkovska, I.; Kaskel, S. Eur. J. Inorg. Chem. 2006, 2006, 4564?4569.[140] Bauer, C. A.; Timofeeva, T. V.; Settersten, T. B.; Patterson, B. D.; Liu, V. H.; Sim-mons, B. A.; Allendorf, M. D. J. Am. Chem. Soc. 2007, 129, 7136?7144.[141] Almutairi, A.; Tham, F. S.; Marsella, M. J. Tetrahedron 2004, 60, 7187?7190.[142] Liu, X.-M.; Lin, T.; Huang, J.; Hao, X.-T.; Ong, K. S.; He, C. Macromolecules 2005,38, 4157?4168.[143] Bai, S.-Q.; Yong, A. M.; Hu, J. J.; Young, D. J.; Zhang, X.; Zong, Y.; Xu, J.; Zuo, J.-L.;Hor, T. S. A. CrystEngComm 2012, 14, 961?971.[144] Schoenecker, P. M.; Carson, C. G.; Jasuja, H.; Flemming, C. J. J.; Walton, K. S. Ind.Eng. Chem. Res. 2012, 51, 6513?6519.[145] Software, C. TOPAS-Academic Version 4.2.[146] Dai, Q.; Liu, W.; Zeng, L.; Lee, C.-S.; Wu, J.; Wang, P. CrystEngComm 2011, 13,4617?4624.[147] Li, Y.; Vamvounis, G.; Holdcroft, S. Macromolecules 2002, 35, 6900?6906.[148] Xue, M.; Zhu, G.; Zhang, Y.; Fang, Q.; Hewitt, I. J.; Qiu, S. Cryst. Growth Des. 2008,8, 427?434.[149] Xiong, S.; Li, S.; Wang, S.; Wang, Z. CrystEngComm 2011, 13, 7236?7245.[150] Zang, S.-Q.; Liang, R.; Fan, Y.-J.; Hou, H.-W.; Mak, T. C. W. Dalton Trans. 2010, 39,8022?8032.145Bibliography[151] Yang, G.-P.; Wang, Y.-Y.; Zhang, W.-H.; Fu, A.-Y.; Liu, R.-T.; Lermontova, E. K.;Shi, Q.-Z. CrystEngComm 2010, 12, 1509?1517.[152] Liu, J.-Q.; Wang, Y.-Y.; Zhang, Y.-N.; Liu, P.; Shi, Q.-Z.; Batten, S. R. Eur. J. Inorg.Chem. 2009, 2009, 147?154.[153] Li, X.-L.; Liu, G.-Z.; Xin, L.-Y.; Wang, L.-Y. CrystEngComm 2012, 14, 1729?1736.[154] Burrows, H. D.; de Melo, J. S.; Serpa, C.; Arnaut, L. G.; Monkman, A. P.; Hamblett, I.;Navaratnam, S. J. Chem. Phys. 2001, 115, 9601?9606.[155] Jeong, S.; Song, X.; Jeong, S.; Oh, M.; Liu, X.; Kim, D.; Moon, D.; Lah, M. S. Inorg.Chem. 2011, 50, 12133?12140.[156] Mart??nez Casado, F. J.; Fabelo, O.; Rodr??guez-Velamaza?n, J. A.; Ramos Riesco, M.;Rodr??guez Cheda, J. A.; Labrador, A.; Rodr??guez-Blanco, C.; Campo, J.; Sa?nchez-Alarcos, V.; Mu?ller, H. Cryst. Growth Des. 2011, 11, 4080?4089.[157] Garc??a-Couceiro, U.; Castillo, O.; Cepeda, J.; Lanchas, M.; Luque, A.; Pe?rez-Ya?n?ez, S.;Roma?n, P.; Vallejo-Sa?nchez, D. Inorg. Chem. 2010, 49, 11346?11361.[158] Manna, S. C.; Zangrando, E.; Drew, M. G. B.; Ribas, J.; Chaudhuri, N. R. Eur. J. Inorg.Chem. 2006, 2006, 481?490.[159] Ma, L.-F.; Wang, L.-Y.; Wang, Y.-Y.; Du, M.; Wang, J.-G. CrystEngComm 2009, 11,109?117.[160] Wang, X.-W.; Dong, Y.-R.; Zheng, Y.-Q.; Chen, J.-Z. Cryst. Growth Des. 2007, 7, 613?615.[161] Kar, P.; Haldar, R.; Go?mez-Garc??a, C. J.; Ghosh, A. Inorg. Chem. 2012, 51, 4265?4273.[162] Liu, D.; Zhou, Q.; Chen, Y.; Yang, F.; Yu, Y.; Shi, Z.; Feng, S. Cryst. Growth Des. 2010,10, 2661?2667.[163] Zhu, Q.-Y.; Wang, J.-P.; Qin, Y.-R.; Shi, Z.; Han, Q.-H.; Bian, G.-Q.; Dai, J. DaltonTrans. 2011, 40, 1977?1983.[164] Zhao, W.; Song, Y.; Okamura, T.-a.; Fan, J.; Sun, W.-Y.; Ueyama, N. Inorg. Chem. 2005,44, 3330?3336.[165] Li, W.; Barton, P. T.; Kiran, M. S. R. N.; Burwood, R. P.; Ramamurty, U.;Cheetham, A. K. Chem. Eur. J. 2011, 17, 12429?12436.[166] Yang, Q.; Zhao, J.-P.; Hu, B.-W.; Zhang, X.-F.; Bu, X.-H. Inorg. Chem. 2010, 49, 3746?3751.[167] Han, S.; Manson, J. L.; Kim, J.; Miller, J. S. Inorg. Chem. 2000, 39, 4182?4185.146Bibliography[168] Cheng, L.; Zhang, W.-X.; Ye, B.-H.; Lin, J.-B.; Chen, X.-M. Eur. J. Inorg. Chem. 2007,2668?2676.[169] Schaate, A.; Schulte, M.; Wiebcke, M.; Godt, A.; Behrens, P. Inorg. Chim. Acta 2009,362, 3600?3606.[170] Zhai, Q.-G.; Zeng, R.-R.; Li, S.-N.; Jiang, Y.-C.; Hu, M.-C. CrystEngComm 2013, 15,965?976.[171] Cai, Y.; Zhang, Y.; Huang, Y.; Marder, S. R.; Walton, K. S. Cryst. Growth Des. 2012,12, 3709?3713.[172] Gu, J.-M.; Kwon, T.-H.; Park, J.-H.; Huh, S. Dalton Trans. 2010, 39, 5608?5610.[173] Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O?Keeffe, M.; Yaghi, O. M.Science 2002, 295, 469?472.[174] Shi, Z.-Q.; Li, Y.-Z.; Guo, Z.-J.; Zheng, H.-G. Cryst. Growth Des. 2013, 13, 3078?3086.[175] Weinberger, D. A.; Higgins, T. B.; Mirkin, C. A.; Stern, C. L.; Liable-Sands, L. M.;Rheingold, A. L. J. Am. Chem. Soc. 2001, 123, 2503?2516.[176] Frey, J.; Bond, A. D.; Holmes, A. B. Chem. Commun. 2002, 0, 2424?2425.[177] Kahn, O. Molecular Magnetism; WILEY-VCH, 1993.[178] Sinnokrot, M. O.; Valeev, E. F.; Sherrill, C. D. J. Am. Chem. Soc. 2002, 124, 10887?10893.[179] Ortmann, F.; Bechstedt, F.; Schmidt, W. G. Phys. Rev. B 2006, 73, 205101.[180] Hulvey, Z.; Furman, J. D.; Turner, S. A.; Tang, M.; Cheetham, A. K. Cryst. Growth Des.2010, 10, 2041?2043.[181] Wang, S.; He, X.; Song, L.; Wang, Z. Synlett 2009, 447?450.[182] Van Bolhuis, F.; Wynberg, H.; Havinga, E. E.; Meijer, E. W.; Staring, E. G. J. Synth.Met. 1989, 30, 381?389.[183] Berg, J. M.; Spira, D. J.; Hodgson, K. O.; Bruce, A. E.; Miller, K. F.; Corbin, J. L.;Stiefel, E. I. Inorg. Chem. 1984, 23, 3412?3418.[184] Bryce, M. R. J. Mater. Chem. 1995, 5, 1481?1496.[185] Geranmayeh, S.; Abbasi, A.; Skripkin, M. Y.; Badiei, A. Polyhedron 2012, 45, 204?212.[186] Carlin, R. L. Magnetochemistry; Springer: Berlin, 1986.[187] Fisher, M. E. Am. J. Phys 1964, 32, 343?346.147Bibliography[188] Menage, S.; Vitols, S. E.; Bergerat, P.; Codjovi, E.; Kahn, O.; Girerd, J. J.; Guillot, M.;Solans, X.; Calvet, T. Inorg. Chem. 1991, 30, 2666?2671.[189] Baca, S. G.; Malaestean, I. L.; Keene, T. D.; Adams, H.; Ward, M. D.; Hauser, J.;Neels, A.; Decurtins, S. Inorg. Chem. 2008, 47, 11108?11119.[190] Hsu, K.-F.; Wang, S.-L. Inorg. Chem. 2000, 39, 1773?1778.[191] Dzyaloshinsky, I. J. Phys. Chem. Solids 1958, 4, 241?255.[192] Moriya, T. Phys. Rev. 1960, 120, 91?98.[193] Barrios, L.; Ribas, J.; Arom??, G.; Ribas-Arin?o, J.; Gamez, P.; Roubeau, O.; Teat, S. J.Inorg. Chem. 2007, 46, 7154?7162.[194] Abdou, H. E.; Mohamed, A. A.; Fackler, J. P. In Gold Chemistry; Mohr, F., Ed.; Wiley-VCH Verlag, 2009; Chapter 1, pp 1?45.[195] Raptis, R. G.; Fackler, J. P. Inorg. Chem. 1988, 27, 4179?4182.[196] Zhan, S.-Z.; Li, M.; Zhou, X.-P.; Li, D.; Weng Ng, S. RSC Adv. 2011, 1, 1457?1459.[197] Lo, S.-C.; Burn, P. L. Chem. Rev. 2007, 107, 1097?1116.[198] Abdou, H. E.; Mohamed, A. A.; Jr., J. P. F.; Burini, A.; Galassi, R.; de Luzuriaga, J.M. L.; Olmos, M. E. Coord. Chem. Rev. 2009, 253, 1661?1669.[199] Pyykko?, P. Angew. Chem. Int. Ed. 2004, 43, 4412?4456.[200] Hsu, C.-W.; Lin, C.-C.; Chung, M.-W.; Chi, Y.; Lee, G.-H.; Chou, P.-T.; Chang, C.-H.;Chen, P.-Y. J. Am. Chem. Soc. 2011, 133, 12085?12099.[201] Osawa, M.; Hoshino, M.; Hashizume, D. Chem. Phys. Lett. 2007, 436, 89?93.[202] Lo?pez-de Luzuriaga, J. M.; Monge, M.; Olmos, M. E.; Pascual, D.; Rodr??guez-Castillo, M. Inorg. Chem. 2011, 50, 6910?6921.[203] Gong, F.; Wang, Q.; Chen, J.; Yang, Z.; Liu, M.; Li, S.; Yang, G.; Bai, L.; Liu, J.;Dong, Y. Inorg. Chem. 2010, 49, 1658?1666.[204] Powell, A. B.; Bielawski, C. W.; Cowley, A. H. J. Am. Chem. Soc. 2009, 131, 18232?18233.[205] Lardies, N.; Romeo, I.; Cerrada, E.; Laguna, M.; Skabara, P. J. Dalton Trans. 2007,5329?5338.[206] Kuchison, A. M.; Wolf, M. O.; Patrick, B. O. Inorg. Chem. 2010, 49, 8802?8812.[207] Uson, R.; Laguna, A.; Vicente, J. J. Organomet. Chem. 1977, 131, 471?475.148[208] Higuchi, H.; Nakayama, T.; Koyama, H.; Ojima, J.; Wada, T.; Sasabe, H. Bull. Chem.Soc. Jpn. 1995, 68, 2363?2377.[209] Allin, S. M.; Barton, W. R.; Bowman, W. R.; (ne?e Mann), E. B.; Elsegood, M. R.;McInally, T.; McKee, V. Tetrahedron 2008, 64, 7745?7758.[210] Becke, A. D. J. Chem. Phys. 1993, 98, 5648?5652.[211] Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785?789.[212] Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270?283.[213] Wadt, W. R.; Hay, P. J. J. Chem. Phys. 1985, 82, 284?298.[214] Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 299?310.[215] Hariharan, P.; Pople, J. Mol. Phys. 1974, 27, 209?214.[216] Cundari, T. R.; Stevens, W. J. J. Chem. Phys. 1993, 98, 5555?5565.[217] Stevens, W. J.; Krauss, M.; Basch, H.; Jasien, P. G. Can. J. Chem 1992, 70, 612?630.[218] Stevens, W. J.; Basch, H.; Krauss, M. J. Chem. Phys. 1984, 81, 6026?6033.[219] Frisch, M. J. et al. Gaussian 09 Revision A.1. 2009.[220] Ovejero, P.; Mayoral, M. J.; Cano, M.; Lagunas, M. C. J. Organomet. Chem. 2007, 692,1690?1697.[221] Wasserberg, D.; Marsal, P.; Meskers, S. C. J.; Janssen, R. A. J.; Beljonne, D. J. Phys.Chem. B 2005, 109, 4410?4415.[222] Xu, B.; Holdcroft, S. J. Am. Chem. Soc. 1993, 115, 8447?8448.[223] Bellete?te, M.; Ce?sare, N. D.; Leclerc, M.; Durocher, G. Chem. Phys. Lett. 1996, 250,31?39.[224] Becker, R. S.; de Melo, J. S.; Mac?anita, A. L.; Elisei, F. Pure Appl. Chem. 1995, 67,9?16.[225] Bobacka, J.; Ivaska, A. Synth. Met. 1991, 43, 3053?3058.[226] Li, M.; Dinca?, M. J. Am. Chem. Soc. 2011, 133, 12926?12929.149Appendix AX-Ray Dataa)b)Figure A.1: Solid state molecular structures of a) 76 and b) 79. Hydrogens and disorder in 76have been omitted for clarity. Ellipsoids are shown at 50 % probability.150Appendix A. X-Ray DataFigure A.2: Solid state molecular structure of 82. Hydrogens and non-coordination solventhave been omitted for clarity. Ellipsoids are shown at 50 % probability.Figure A.3: Solid state molecular structure of 93. Hydrogens and non-coordination solventhave been omitted for clarity. Ellipsoids are shown at 50 % probability.151AppendixA.X-RayDataTable A.1: Selected crystallographic data for 71 ? 73.71 72 73Formula C19H25N3O7S2Zn C20H26N2O6S2Zn C16H22O7S5ZnCrystal color, shape colorless, plate colorless, prism colorless, prismDimensions / mm 0.50 ? 0.30 ? 0.03 0.40 ? 0.35 ? 0.15 0.60 ? 0.40 ? 0.15Temperature / K 100 100 100Crystal system Monoclinic Monoclinic MonoclinicSpace group P21/c Cc Cca / ? 6.5669(2) 6.7609(2) 6.7493(6)b / ? 22.5540(12) 18.5954(5) 24.486(2)c / ? 16.1681(8) 18.7721(5) 14.051(2)? / deg 90 90 90? / deg 93.051(2) 93.844(2) 94.733(4)? / deg 90 90 90V / ?3 2391.3(2) 2354.8(2) 2314.2(3)Z 4 4 42? (max) / deg 56.18 56.03 56.64Total reflections 34710 20409 20851Unique reflections 5966 5480 5530?calc / g cm?3 1.491 1.467 1.584? (k?) / mm?1 12.45 12.58 15.46R1a (I>2.00?(I)) 0.0347 0.0289 0.0183?R2a (I>2.00?(I)) 0.0823 0.0748 0.0457Goodness of fit 1.029 1.041 1.024a Function minimized. ??(|Fo|?Fc|)2, R1=? ||Fo| ? |Fc||/?|Fo|, ?R2=[?(?(|Fo| ? |Fc|)2)/??(|Fo|)2]1/2152AppendixA.X-RayDataTable A.2: Selected crystallographic data for 74 ? 77.74 75 76 77Formula C57H59N5O11S4Zn2 C24H35NO4S2Zn C15H8NO4S2Zn C33H30N3O7S2ZnCrystal color, shape colorless, rod colorless, rod colorless, needle colorless, rodDimensions / mm 0.35 ? 0.20 ? 0.10 0.10 ? 0.04 ? 0.02 0.50 ? 0.04 ? 0.02 0.22 ? 0.10 ? 0.08Temperature / K 100 100 100 100Crystal system Monoclinic Monoclinic Monoclinic TriclinicSpace group P21/n P21/n C2/c P-1a / ? 16.3642(6) 7.503(3) 19.4124(18) 9.8812(9)b / ? 17.0748(6) 18.281(6) 20.2951(18) 12.9947(13)c / ? 20.6230(7) 19.375(6) 13.8736(13) 13.7435(14)? / deg 90 90 90 71.730(6)? / deg 90.226(2) 100.470(15) 118.414(2) 87.319(6)? / deg 90 90 90 77.841(6)V / ?3 5762.3(4) 2613.3(16) 4797(2) 1637.8(3)Z 4 4 8 22? (max) / deg 60.2 45.2 45.1 52.8Total reflections 99492 11499 7303 24692Unique reflections 16899 3392 3128 6719?calc / g cm?3 1.44 1.35 1.067 1.440? (k?) / mm?1 1.041 1.128 1.223 0.929R1a (I>2.00?(I)) 0.0525 0.0638 0.0820 0.0384?R2a (I>2.00?(I)) 0.1425 0.1788 0.2452 0.0837Goodness of fit 1.101 0.952 1.068 1.028a Function minimized. ??(|Fo|?Fc|)2, R1=? ||Fo| ? |Fc||/?|Fo|, ?R2=[?(?(|Fo| ? |Fc|)2)/??(|Fo|)2]1/2153AppendixA.X-RayDataTable A.3: Selected crystallographic data for 79 ? 82.79 80 81 82Formula C16H9NO4SsZn C40H36N4O6S2Zn C201H257N15O32S12Zn6 C14H18N2O4SZn0.5Crystal color, shape yellow, rod colorless, prism colorless, prism yellow, prismDimensions / mm 0.25 ? 0.10 ? 0.07 0.70 ? 0.30 ? 0.25 0.25 ? 0.18 ?0.13 0.20 ? 0.10 ? 0.10Temperature / K 100 100 100 100Crystal system Monoclinic Triclinic Monoclinic MonoclinicSpace group C2/c P-1 C2/c C2/ca / ? 17.1764(8) 8.6855(15) 31.138(2) 29.0876(16)b / ? 22.0141(12) 12.7109(18) 39.627(2) 6.1875(4)c / ? 9.9312(5) 18.183(3) 22.721(2) 17.3626(10)? / deg 90 91.810(8) 90 90? / deg 96.535(2) 102.910(15) 121.737(2) 99.1020(10)? / deg 90 106.455(8) 90 90V / ?3 3730.8(3) 1866.8(5) 23844(3) 3085.6(3)Z 8 2 4 82? (max) / deg 60.0 46.6 52.6 59.9Total reflections 20695 19657 94733 18754Unique reflections 5555 5356 24815 4866?calc / g cm?3 1.455 1.420 1.162 1.477? (k?) / mm?1 1.557 0.823 0.761 0.986R1a (I>2.00?(I)) 0.0420 0.0515 0.0542 0.0275?R2a (I>2.00?(I)) 0.1102 0.1314 0.1611 0.0698Goodness of fit 0.962 1.017 1.078 1.035a Function minimized. ??(|Fo|?Fc|)2, R1=? ||Fo| ? |Fc||/?|Fo|, ?R2=[?(?(|Fo| ? |Fc|)2)/??(|Fo|)2]1/2154AppendixA.X-RayDataTable A.4: Selected crystallographic data for 85 and 92?94.85 92 93 94Formula C32H29N2O6.5S3Zn C22H26N2O8S2Mn C30H31N2O7S2Cu C71H95.5Mn3N1.5O16S6Crystal color, shape orange, rod colorless, rod green, prism colorless, prismDimensions / mm 0.15 ? 0.06 ? 0.04 0.17 ? 0.04 ? 0.02 0.12 ? 0.11 ? 0.10 0.31 ? 0.26 ? 0.06Temperature / K 90 90 90 90Crystal system Triclinic Orthorhombic Monoclinic OrthorhombicSpace group P-1 Pbcn P2/n C2221a / ? 9.9037(15) 26.6207(10) 16.959(6) 18.515(2)b / ? 10.0679(15) 25.8330(10) 8.997(3) 57.377(5)c / ? 33.184(5) 9.0398(4) 19.447(6) 48.822(5)? / deg 91.180(4) 90 90 90? / deg 90.026(4) 90 92.422(5) 90? / deg 108.872(4) 90 90 90V / ?3 3130.1(8) 6216.6(4) 2964.6(17) 51886(9)Z 4 12 4 162? (max) / deg 60.50 119.20 45.2 112.50Total reflections 57521 29666 8690 33113Unique reflections 18011 4340 4426 20159?calc / g cm?3 1.501 1.38 1.477 0.811? (k?) / mm?1 1.034 5.148 0.928 3.553R1a (I>2.00?(I)) 0.0751 0.0706 0.0658 0.0886?R2a (I>2.00?(I)) 0.1562 0.1862 0.1659 0.2588Goodness of fit 1.057 1.110 1.129 0.963a Function minimized. ??(|Fo|?Fc|)2, R1=? ||Fo| ? |Fc||/?|Fo|, ?R2=[?(?(|Fo| ? |Fc|)2)/??(|Fo|)2]1/2155AppendixA.X-RayDataTable A.5: Selected crystallographic data for 95?98.95 96 97 98Formula C17.5H18NO7S3Co C14H10O6S3Mn C14H9O5.5S3Mn C32H28N2O6S3MnCrystal color, shape red, prism yellow-orange, plate red-orange, plate yellow-orange, brickDimensions / mm 0.15 ? 0.10 ? 0.05 0.21 ? 0.18 ? 0.04 0.20 ? 0.20 ? 0.02 0.60 ? 0.33 ? 0.12Temperature / K 100 90 90 100Crystal system Monoclinic Orthorhombic Monoclinic TriclinicSpace group C2/c P212121 C2/c P1?a / ? 24.638(2) 6.5962(5) 35.442(8) 9.1891(5)b / ? 16.8906(14) 7.1987(7) 7.6573(16) 10.1201(6)c / ? 10.8936(9) 32.446(2) 11.038(2) 16.8042(10)? / deg 90 90 90 95.405(3)? / deg 107.184(3) 90 97.618(4) 91.005(2)? / deg 90 90 90 97.203(3)V / ?3 4331.0(6) 1540.6(2) 2969.3(11) 1542.79(15)Z 8 4 8 22? (max) / deg 54.24 130.66 54.30 60.24Total reflections 20958 1927 3292 31722Unique reflections 4550 1534 2600 8938?calc / g cm?3 1.563 1.816 1.863 1.48? (k?) / mm?1 1.120 11.059 1.337 0.679R1a (I>2.00?(I)) 0.0590 0.0775 0.0671 0.0288?R2a (I>2.00?(I)) 0.1559 0.2115 0.1729 0.0721Goodness of fit 1.064 1.096 1.054 1.034a Function minimized. ??(|Fo|?Fc|)2, R1=? ||Fo| ? |Fc||/?|Fo|, ?R2=[?(?(|Fo| ? |Fc|)2)/??(|Fo|)2]1/2156AppendixA.X-RayDataTable A.6: Selected crystallographic data for 118, 119, 126, and 131.118 119 126 131Formula C7H6N2S C9H10N2S C21H15N6S3Au3 C45H63N6S3Au3Crystal color, shape colorless, prism colorless, rod colorless, needle colorless, plateDimensions / mm 0.25 ? 0.20 ? 0.15 0.50 ? 0.10 ? 0.06 0.36 ? 0.05 ? 0.02 0.21 ? 0.10 ? 0.02Temperature / K 90 90 90 90Crystal system Orthorhombic Monoclinic Orthorhombic MonoclinicSpace group P212121 C2/c Pca21 C2/ca / ? 5.4837(8) 39.587(8) 25.9877(14) 34.404(5)b / ? 7.4018(10) 6.5987(13) 13.4134(8) 22.375(3)c / ? 16.899(2) 21.304(4) 6.8232(4) 13.0426(19)? / deg 90 90 90 90? / deg 90 106.758(3) 90 103.142(2)? / deg 90 90 90 90V / ?3 685.91(17) 5328.8(18) 2378.5(2) 9777(2)Z 4 24 4 82? (max) / deg 59.78 54.94 54.71 50.63Total reflections 4450 41777 17988 36578Unique reflections 1922 6109 5148 8908?calc / g cm?3 1.454 1.333 2.900 1.868? (k?) / mm?1 0.382 0.307 18.746 9.145R1a (I>2.00?(I)) 0.0282 0.0383 0.0409 0.0612?R2a (I>2.00?(I)) 0.0699 0.1066 0.0750 0.1969Goodness of fit 1.042 1.041 1.042 1.061a Function minimized. ??(|Fo|?Fc|)2, R1=? ||Fo| ? |Fc||/?|Fo|, ?R2=[?(?(|Fo| ? |Fc|)2)/??(|Fo|)2]1/2157Appendix A. X-Ray DataTable A.7: Selected bond lengths (?) and angles (?) of 71.Bond lengthsC2-S1 1.726(2) C5-S1 1.733(2) C6-S2 1.724(2)C9-S2 1.727(2) O2-Zn1 1.9746(15) O5-Zn1 2.4454(17)O6-Zn1 1.9998(15) O7-Zn1 1.9970(16) O8-Zn1 2.0106(16)AnglesO2-Zn1-O7 99.13(6) O2-Zn1-O6 139.15(7)O7-Zn1-O6 108.24(7) O2-Zn1-O8 107.50(7)O7-Zn1-O8 99.80(7) O6-Zn1-O8 97.23(6)O2-Zn1-O5 90.65(6) O7-Zn1-O5 93.88(7)O6-Zn1-O5 58.44(6) O8-Zn1-O5 155.03(6)Torsion AnglesS1-C5-C6-S2 166.18(13)158Appendix A. X-Ray DataTable A.8: Selected bond lengths (?) and angles (?) of 72.Bond lengthsC2-S1 1.730(2) C5-S1 1.734(2) C6-S2 1.729(2C9-S2 1.727(2) O1-Zn1 2.4670(17) O2-Zn1 1.9925(16)O4-Zn1 1.9685(17) O5-Zn1 2.0133(17) O6-Zn1 2.0273(18)AnglesO4-Zn1-O2 140.66(7) O4-Zn1-O5 96.97(7)O2-Zn1-O5 114.05(7) O4-Zn1-O6 105.29(7)O2-Zn1-O6 95.09(7) O5-Zn1-O6 96.35(8)O4-Zn1-O1 96.49(6) O2-Zn1-O1 58.41(6)O5-Zn1-O1 95.80(7) O6-Zn1-O1 153.49(7)Torsion AnglesS1-C5-C6-S2 -168.83(11)Table A.9: Selected bond lengths (?) and angles (?) of 73.Bond lengthsC2-S1 1.7346(16) C5-S1 1.7378(16) C6-S2 1.7303(15)C9-S2 1.7313(16) O2-Zn1 1.9751(13) O3-Zn1 1.9445(12)O5-Zn1 2.0180(13) O6-Zn1 1.9879(13)AnglesO3-Zn1-O2 132.96(5) O3-Zn1-O6 101.14(5)O2-Zn1-O6 113.05(5) O3-Zn1-O5 110.57(5)O2-Zn1-O5 96.58(5) O6-Zn1-O5 97.15(5)Torsion AnglesS1-C5-C6-S2 175.11(9)159Appendix A. X-Ray DataTable A.10: Selected bond lengths (?) and angles (?) of 74.Bond lengthsC2-S2 1.717(3) C5-S2 1.721(3) C6-S1 1.722(3)C9-S1 1.721(3) C24-S4 1.715(3) C27-S4 1.726(3)C28-S3 1.727(3) C31-S3 1.718(3) O1-Zn1 2.071(2)O2-Zn2 2.038(2) O3-Zn1 2.068(2) O4-Zn2 2.057(2)O5-Zn1 2.031(2) O6-Zn2 2.062(2) O7-Zn2 2.064(2)O8-Zn1 2.051(2) Zn1-N1 2.027(3) Zn2-N2 2.025(3)AnglesN1-Zn1-O5 100.01(10) N1-Zn1-O8 103.84(9)O5-Zn1-O8 155.88(8) N1-Zn1-O3 107.13(9)O5-Zn1-O3 90.88(8) O8-Zn1-O3 85.54(8)N1-Zn1-O1 95.40(9) O5-Zn1-O1 88.44(8)O8-Zn1-O1 85.84(8) O3-Zn1-O1 157.22(8)N2-Zn2-O2 100.25(10) N2-Zn2-O4 103.17(10)O2-Zn2-O4 156.41(8) N2-Zn2-O6 94.51(10)O2-Zn2-O6 88.19(9) O4-Zn2-O6 87.24(8)N2-Zn2-O7 107.64(10) O2-Zn2-O7 89.70(8)O4-Zn2-O7 85.89(8) O6-Zn2-O7 157.76(8)Torsion AnglesS2-C5-C6-S1 -110.5(2) S4-C27-C28-S3 56.5(2)Table A.11: Selected bond lengths (?) and angles (?) of 75.Bond lengthsC2-S1 1.736(9) C5-S1 1.697(9) C6-S2 1.718(9)C9-S2 1.750(9) O1-Zn1 2.041(6) O2-Zn1 2.038(6)O3-Zn1 2.047(6) O4-Zn1 2.052(6) Zn1-N1 2.056(8)AnglesO2-Zn1-O1 157.0(2) O2-Zn1-O3 85.1(2)O1-Zn1-O3 88.2(3) . O2-Zn1-O4 88.7(2)O1-Zn1-O4 88.9(3) O3-Zn1-O4 156.9(2)O2-Zn1-N1 108.1(3) O1-Zn1-N1 94.9(3)O3-Zn1-N1 104.6(3) O4-Zn1-N1 98.6(3)Torsion AnglesS1-C5-C6-S2 -68.3(9)160Appendix A. X-Ray DataTable A.12: Selected bond lengths (?) and angles (?) of 76.Bond lengthsC2-S1 1.719(9) C5-S1 1.703(9) C6-S2 1.727(9)C9-S2 1.730(8) O1-Zn1 2.029(6) O2-Zn1 2.030(6)O3-Zn1 2.033(6) O4-Zn1 2.055(6) N1-Zn1 2.063(12)Zn1-N1B 1.985(15)AnglesO1-Zn1-O2 88.2(2) O1-Zn1-O3 161.1(2)O2-Zn1-O3 89.6(2) O1-Zn1-O4 87.2(3)O2-Zn1-O4 157.2(2) O3-Zn1-O4 87.6(2)O1-Zn1-N1 100.3(4) O2-Zn1-N1 107.5(5)O3-Zn1-N1 98.3(4) O4-Zn1-N1 95.3(4)N1B-Zn1-O1 92.0(7) N1B-Zn1-O2 107.9(6)N1B-Zn1-O3 106.5(7) N1B-Zn1-O4 94.6(6)Torsion AnglesS1-C5-C6-S2 173.5(7)Table A.13: Selected bond lengths (?) and angles (?) of 77.Bond lengthsC2-S1 1.725(2) C5-S1 1.733(3) C6-S2 1.729(2)C9-S2 1.724(3) N1-Zn1 2.045(2) O1-Zn1 2.0204(17)O2-Zn1 2.2974(18) O3-Zn1 1.9560(16) Zn1-O5B 2.04(3)Zn1-O5A 2.05(2)AnglesO3-Zn1-O1 146.31(7) O3-Zn1-O5B 96.7(8)O1-Zn1-O5B 94.9(8) O3-Zn1-N1 100.13(7)O1-Zn1-N1 108.66(7) O5B-Zn1-N1 100.5(7)O3-Zn1-O5A 102.0(6) O1-Zn1-O5A 92.4(6)N1-Zn1-O5A 95.5(6) O3-Zn1-O2 100.92(7)O1-Zn1-O2 60.95(6) O5B-Zn1-O2 155.1(7)N1-Zn1-O2 93.56(7) O5A-Zn1-O2 153.4(6)Torsion AnglesS1-C5-C6-S2 -89.9(3) C24-C25-C25-C26 -1.13(4)161Appendix A. X-Ray DataTable A.14: Selected bond lengths (?) and angles (?) of 79.Bond lengthsC2-S1 1.729(5) C5-S1 1.720(5) C6-S2 1.724(5)C9-S2 1.733(5) N1-Zn1 2.024(4) O1-Zn1 2.046(3)O2-Zn1 2.011(4) O3-Zn1 2.096(4) O4-Zn1 2.035(4)AnglesO2-Zn1-N1 97.95(16) O2-Zn1-O4 162.23(15)N1-Zn1-O4 99.10(16) O2-Zn1-O1 87.58(15)N1-Zn1-O1 106.27(16) O4-Zn1-O1 92.41(14)O2-Zn1-O3 86.56(15) N1-Zn1-O3 101.70(16)O4-Zn1-O3 85.13(15) O1-Zn1-O3 151.96(14)sTorsion AnglesS1-C5-C6-S2 145.6(4) C15-C16-C16-C15 180.0Table A.15: Selected bond lengths (?) and angles (?) of 80.Bond lengthsC2-S1 1.728(6) C5-S1 1.731(5) C6-S2 1.725(5)C9-S2 1.711(5) N1-Zn1 2.050(4) N2-Zn1 2.011(4)O1-Zn1 1.969(3) O3-Zn1 1.962(4)AnglesO3-Zn1-O1 110.94(15) O3-Zn1-N2 121.98(17)O1-Zn1-N2 107.80(15) O3-Zn1-N1 96.91(16)O1-Zn1-N1 98.10(16) N2-Zn1-N1 118.46(18)Torsion AnglesS1-C5-C6-S2 -60.0(5) C30-C29-C29-C30 180.0162Appendix A. X-Ray DataTable A.16: Selected bond lengths (?) and angles (?) of 81.Bond lengthsC2-S1 1.712(5) C5-S1 1.710(5) C6-S2 1.722(5)C9-S2 1.712(5) C12-S3 1.710(5) C15-S3 1.724(5)C16-S4 1.720(5) C19-S4 1.719(5) C22-S5 1.708(5)C25-S5 1.723(5) C26-S6 1.722(5) C29-S6 1.709(5)N1-Zn1 2.039(4) N2-Zn3 1.999(4) N3-Zn2 2.010(4)N4-Zn1 2.046(4) O1-Zn1 2.387(3) O2-Zn1 2.021(3)O3-Zn3 2.056(3) O4-Zn2 2.052(4) O5-Zn1 1.934(3)O7-Zn3 2.088(4) O8-Zn2 2.037(3) O9-Zn3 2.019(3)O10-Zn2 2.056(3) O11-Zn3 2.017(3) O12-Zn2 2.027(3)AnglesO5-Zn1-O2 118.63(14) O5-Zn1-N1 105.52(14)O2-Zn1-N1 98.18(15) O5-Zn1-N4 125.78(15)O2-Zn1-N4 103.44(15) N1-Zn1-N4 100.23(14)O5-Zn1-O1 85.94(12) O2-Zn1-O1 59.16(13)N1-Zn1-O1 157.26(15) N4-Zn1-O1 88.07(13)N3-Zn2-O12 97.66(16) N3-Zn2-O8 105.55(17)O12-Zn2-O8 91.28(14) N3-Zn2-O4 97.75(16)O12-Zn2-O4 87.08(14) O8-Zn2-O4 156.64(14)N3-Zn2-O10 100.96(16) O12-Zn2-O10 161.11(14)O8-Zn2-O10 86.78(14) O4-Zn2-O10 87.32(14)N2-Zn3-O11 98.91(15) N2-Zn3-O9 103.01(15)O11-Zn3-O9 158.01(14) N2-Zn3-O3 98.80(15)O11-Zn3-O3 90.50(13) O9-Zn3-O3 87.93(14)N2-Zn3-O7 99.47(15) O11-Zn3-O7 87.98(14)O9-Zn3-O7 86.69(14) O3-Zn3-O7 161.68(13)Torsion AnglesC35-C36-C37-C38 -168.7(4) C47-C48-C49-C50 -178.5 (3)S1-C5-C6-S2 118.4(3) S3-C15-C16-S4 65.4(3)S5-C25-C26-S6 117.6 (4)163Appendix A. X-Ray DataTable A.17: Selected bond lengths (?) and angles (?) of 82.Bond lengthsC2-S1 1.7259(14) O2-Zn1 1.9566(10) O3-Zn1 1.9821(10)AnglesO2-Zn-O2 100.36(6) O2-Zn1-O3 104.47(4)O2-Zn1-O3 118.25(4) O3-Zn1-O3 111.24(6)Torsion AnglesS1-C5-C6-C8 32.88(18)Table A.18: Selected bond lengths (?) and angles (?) of 85.Bond lengthsC2-S1 1.714(9) C5-S1 1.737(9) C6-S2 1.727(10)C9-S2 1.733(10) C10-S3 1.743(9) C13-S3 1.730(10)O1-Zn1 2.296(8) O2-Zn1 2.048(7) O3-Zn2 1.999(7)O5-Zn2 2.131(7) O6-Zn2 2.205(7) O7-Zn1 1.940(7)O9-Zn1 2.010(7) O10-Zn1 1.995(8) O11-Zn2 2.146(8)O12-Zn2 2.113(8) O13-Zn2 2.066(7)AnglesO7-Zn1-O10 94.6(3) O7-Zn1-O9 102.3(3)O10-Zn1-O9 94.6(3) O7-Zn1-O2 147.0(3)O10-Zn1-O2 109.7(3) O9-Zn1-O2 97.8(3)O7-Zn1-O1 95.9(3) O10-Zn1-O1 95.0(3)O9-Zn1-O1 158.6(3) O2-Zn1-O1 61.0(3)O3-Zn2-O13 100.3(3) O3-Zn2-O12 85.9(3)O13-Zn2-O12 85.9(3) O3-Zn2-O5 164.5(3)O13-Zn2-O5 95.1(3) O12-Zn2-O5 96.7(3)O3-Zn2-O11 90.2(3) O13-Zn2-O11 89.7(3)O12-Zn2-O11 173.5(3) O5-Zn2-O11 88.4(3)O3-Zn2-O6 103.7(3) O13-Zn2-O6 155.3(3)O12-Zn2-O6 90.3(3) O5-Zn2-O6 61.1(3)O11-Zn2-O6 95.8(3)Torsion AnglesS1-C5-C6-S2 175.4(6) S2-C9-C10-S3 161.5(5)S4-C31-C32-S5 -174.2(5) S5-C35-C36-S6 -150.7(6)164Appendix A. X-Ray DataTable A.19: Selected bond lengths (?) and angles (?) of 92.Bond lengthsC2-S1 1.724(6) C5-S1 1.724(6) C6-S2 1.729(6)C9-S2 1.707(6) O1-Mn1 2.173(4) O5-Mn1 2.183(5)O6-Mn1 2.243(5) O3-Mn2 2.179(4) Mn2-O4B 2.211(13)Mn2-O4 2.25(2) Mn2-O8 2.124(5)AnglesO1-Mn1-O1 176.5(2) O1-Mn1-O5 91.42(16)O1-Mn1-O5 86.18(16) O5-Mn1-O5 93.1(3)O1-Mn1-O6 88.97(16) O1-Mn1-O6 93.55(16)O5-Mn1-O6 177.3(2) O5-Mn1-O6 89.7(2)O6-Mn1-O6 87.6(3) O8-Mn2-O4 83.4(6)O8-Mn2-O3 82.72(18) O4-Mn2-O3 95.7(6)O8-Mn2-O4B 93.0(4) O3-Mn2-O4B 90.4(4)Torsion AnglesS1-C5-C6-S2 122.49(2)Table A.20: Selected bond lengths (?) and angles (?) of 93.Bond lengthsC2-S1 1.706(9) C5-S1 1.691(10) C6-S2 1.712(9)C9-S2 1.695(10) O1-Cu1 1.985(6) O2-Cu1 1.985(6)O3-Cu1 1.955(6) O4-Cu1 1.947(6) O5-Cu1 2.132(6)AnglesO4-Cu1-O3 168.0(3) O4-Cu1-O1 88.8(2)O3-Cu1-O1 89.1(3) O4-Cu1-O2 87.4(2)O3-Cu1-O2 92.4(3) O1-Cu1-O2 168.2(3)O4-Cu1-O5 96.4(3) O3-Cu1-O5 95.6(3)O1-Cu1-O5 101.4(3) O2-Cu1-O5 90.2(3)Torsion AnglesS1-C5-C5-S1 -98.6(8) S2-C6-C6-S2 46.1(8)165Appendix A. X-Ray DataTable A.21: Selected bond lengths (?) and angles (?) of 94.Bond lengthsC2-S1 1.688(8) C5-S1 1.720(7) C6-S2 1.742(8)C9-S2 1.714(8) C24-S3 1.699(8) C27-S3 1.718(8)C28-S4 1.693(7) C31-S4 1.723(9) C46-S5 1.651(9)C49-S5 1.770(9) C50-S6 1.722(9) C53-S6 1.689(8)C68-S7 1.665(10) C71-S7 1.669(11) C72-S8 1.767(10)C75-S8 1.721(10) C90-S9 1.694(9) C93-S9 1.749(11)C94-S10 1.663(13) C97-S10 1.774(8) C112-S11 1.675(8)C115-S11 1.761(10) C116-S12 1.783(10) C119-S12 1.670(8)O1-Mn1 2.243(6) O2-Mn2 2.221(7) O2-Mn1 2.274(6)O3-Mn5 2.149(6) O4-Mn6 2.026(6) O5-Mn2 2.160(6)O6-Mn3 1.994(6) O7-Mn4 2.270(6) O8-Mn5 2.181(6)O8-Mn4 2.289(5) O9-Mn1 2.062(7) O10-Mn2 2.139(8)O11-Mn2 2.214(7) O11-Mn3 2.313(6) O12-Mn3 2.191(6)O13-Mn2 2.156(7) O14-Mn3 2.090(12) O15-Mn6 2.021(8)O16-Mn5 2.164(5) O17-Mn5 2.175(7) O18-Mn4 2.080(8)O19-Mn1 2.124(8) O20-Mn2 2.177(6) O21-Mn6 2.218(7)O22-Mn5 2.171(6) O22-Mn6 2.296(6) O23-Mn5 2.163(7)O24-Mn4 2.060(7) O25-Mn4 2.139(8) O27-Mn4 2.155(8)O28-Mn6 2.119(9) O29-Mn1 2.212(9) O30-Mn6 2.222(9)O31-Mn1 2.136(10) O32-Mn3 2.305(12) O33-Mn3 1.813(19)AnglesO9-Mn1-O19 89.5(3) O9-Mn1-O31 112.6(4) O19-Mn1-O31 91.6(4)O9-Mn1-O29 89.2(3) O19-Mn1-O29 176.4(3) O31-Mn1-O29 85.8(4)O9-Mn1-O1 150.7(2) O19-Mn1-O1 94.9(3) O31-Mn1-O1 96.3(3)O29-Mn1-O1 87.9(3) O9-Mn1-O2 92.7(2) O19-Mn1-O2 96.8(3)O31-Mn1-O2 153.4(3) O29-Mn1-O2 86.7(3) O1-Mn1-O2 57.97(19)O10-Mn2-O13 90.5(3) O10-Mn2-O5 177.0(3) O13-Mn2-O5 89.8(2)O10-Mn2-O20 89.4(3) O13-Mn2-O20 176.9(3) O5-Mn2-O20 90.5(3)O10-Mn2-O11 89.1(3) O13-Mn2-O11 96.0(3) O5-Mn2-O11 87.9(2)O20-Mn2-O11 87.1(2) O10-Mn2-O2 92.8(3) O13-Mn2-O2 85.1(3)O5-Mn2-O2 90.2(2) O20-Mn2-O2 91.8(2) O11-Mn2-O2 177.8(3)O33-Mn3-O6 86.9(5) O33-Mn3-O14 178.7(6) O6-Mn3-O14 92.7(5)O33-Mn3-O12 84.2(5) O6-Mn3-O12 151.1(3) O14-Mn3-O12 96.7(4)O33-Mn3-O32 91.5(5) O6-Mn3-O32 112.0(4) O14-Mn3-O32 87.5(4)O12-Mn3-O32 95.7(3) O33-Mn3-O11 89.3(5) O6-Mn3-O11 93.1(2)O14-Mn3-O11 91.9(4) O12-Mn3-O11 59.4(2) O32-Mn3-O11 154.9(3)O24-Mn4-O18 93.8(3) O24-Mn4-O25 108.7(3) O18-Mn4-O25 88.8(3)O24-Mn4-O27 87.8(3) O18-Mn4-O27 174.8(3) O25-Mn4-O27 86.0(3)O24-Mn4-O7 151.5(2) O18-Mn4-O7 94.3(3) O25-Mn4-O7 98.7(3)O27-Mn4-O7 86.6(3) O24-Mn4-O8 94.1(2) O18-Mn4-O8 94.3(3)O25-Mn4-O8 156.7(3) O27-Mn4-O8 90.6(3) O7-Mn4-O8 58.11(19)O3-Mn5-O23 178.5(3) O3-Mn5-O16 90.0(2) O23-Mn5-O16 89.9(2)O3-Mn5-O22 91.6(2) O23-Mn5-O22 89.9(2) O16-Mn5-O22 93.4(2)166Appendix A. X-Ray DataTable A.21: Selected bond lengths (?) and angles (?) of 94.O3-Mn5-O17 92.2(2) O23-Mn5-O17 87.9(2) O16-Mn5-O17 177.6(3)O22-Mn5-O17 87.6(2) O3-Mn5-O8 87.4(2) O23-Mn5-O8 91.1(2)O16-Mn5-O8 85.4(2) O22-Mn5-O8 178.5(2) O17-Mn5-O8 93.6(2)O15-Mn6-O4 94.0(3) O15-Mn6-O28 87.2(3) O4-Mn6-O28 109.9(3)O15-Mn6-O21 95.1(3) O4-Mn6-O21 149.5(3) O28-Mn6-O21 99.5(3)O15-Mn6-O30 173.1(3) O4-Mn6-O30 91.2(3) O28-Mn6-O30 86.7(4)O21-Mn6-O30 82.7(3) O15-Mn6-O22 96.2(3) O4-Mn6-O22 90.8(2)O28-Mn6-O22 158.8(3) O21-Mn6-O22 59.4(2) O30-Mn6-O22 88.3(3)Torsion AnglesS1-C5-C6-S2 56.4(5)S3-C27-C28-S451.6(6)S5-C49-C50-S6-59.8(6)S7-C71-C72-S882.7(6)S9-C93-C94-S10-101.8(5)S11-C115-C116-S12-54.9(7)Table A.22: Selected bond lengths (?) and angles (?) of 95.Bond lengthsC2-S1 1.731(5) C4-S2 1.743(5) C5-S1 1.713(5)C6-S3 1.715(5) C7-S2 1.746(5) C9-S3 1.731(5)N1-Co1 2.112(3) O1-Co1 2.044(4) O2-Co1 2.082(3)O4-Co1 2.100(3) O5-Co1 2.115(3) O6-Co1 2.089(4)AnglesO1-Co1-O2 95.18(15) O1-Co1-O6 178.23(16)O2-Co1-O6 86.55(16) O1-Co1-O4 85.82(14)O2-Co1-O4 175.74(14) O6-Co1-O4 92.49(15)O1-Co1-N1 91.31(14) O2-Co1-N1 90.30(14)O6-Co1-N1 89.08(16) O4-Co1-N1 85.53(14)O1-Co1-O5 86.94(12) O2-Co1-O5 93.92(14)O6-Co1-O5 92.54(14) O4-Co1-O5 90.26(14)N1-Co1-O5 175.56(12)Torsion AnglesS2-C4-C5-S1 -178.6(3) S1-C5-C6-S3 -5.8(10)S3-C6-C7-S2 -175.3(3)167Appendix A. X-Ray DataTable A.23: Selected bond lengths (?) and angles (?) of 96.Bond lengthsC2-S1 1.738(14) C5-S1 1.703(12) C6-S2 1.726(13)C9-S2 1.778(16) C10-S3 1.708(15) C13-S3 1.697(12)O1-Mn1 2.141(9) O2-Mn1 2.181(8) O3-Mn1 2.147(9)O4-Mn1 2.195(9) O5-Mn1 2.207(10) O6-Mn1 2.178(9)AnglesO1-Mn1-O3 176.1(3) O1-Mn1-O6 88.3(4)O3-Mn1-O6 89.9(4) O1-Mn1-O2 88.2(4)O3-Mn1-O2 95.5(3) O6-Mn1-O2 100.1(4)O1-Mn1-O4 89.6(3) O3-Mn1-O4 86.8(3)O6-Mn1-O4 84.8(4) O2-Mn1-O4 174.5(4)O1-Mn1-O5 95.4(4) O3-Mn1-O5 86.1(4)O6-Mn1-O5 173.6(4) O2-Mn1-O5 85.2(4)O4-Mn1-O5 90.0(4)Torsion AnglesS1-C5-C6-S2 157.9(9) S2-C9-C10-S3 19.8(9)Table A.24: Selected bond lengths (?) and angles (?) of 97.Bond lengthsC2-S1 1.739(8) C5-S1 1.728(7) C6-S2 1.746(7)C9-S2 1.739(8) C10-S3 1.724(8) C13-S3 1.727(8)O1-Mn1 2.144(5) O2-Mn1 2.120(5) O4-Mn1 2.199(5)O4-Mn1 2.225(5) O5-Mn1 2.262(4) O6-Mn1 2.157(5)AnglesMn1-O4 Mn1 99.55(19) Mn1-O5 Mn1 111.1(3)O2-Mn1-O1 100.2(2) O2-Mn1-O6 96.1(2)O1-Mn1-O6 91.7(2) O2-Mn1-O4 167.4(2)O1-Mn1-O4 92.23(19) O6-Mn1-O4 85.53(19)O2-Mn1-O4 87.02(19) O1-Mn1-O4 171.99(19)O6-Mn1-O4 90.99(19) O4-Mn1-O4 80.45(19)O2-Mn1-O5 87.66(16) O1-Mn1-O5 90.71(18)O6-Mn1-O5 175.11(19) O4-Mn1-O5 90.11(16)O4-Mn1-O5 86.09(17)Torsion AnglesS1-C5-C6-S2 179.2(4) S2-C9-C10-S3 -178.8(4)168Appendix A. X-Ray DataTable A.25: Selected bond lengths (?) and angles (?) of 98.Bond lengthsC2-S1 1.7229(12) C5-S1 1.7302(11) C6-S2 1.7281(12)C9-S2 1.7307(12) C10-S3 1.7219(12) C13-S3 1.7248(12)O1-Mn1 2.3322(9) O2-Mn1 2.2339(9) O3-Mn1 2.1296(9)O4-Mn1 2.1367(9) O5-Mn1 2.1632(9) O6-Mn1 2.1499(10)AnglesO3-Mn1-O4 100.01(4) O3-Mn1-O6 84.73(4)O4-Mn1-O6 175.02(4) O3-Mn1-O5 104.56(4)O4-Mn1-O5 91.22(4) O6-Mn1-O5 86.06(4)O3-Mn1-O2 148.61(3) O4-Mn1-O2 86.55(4)O6-Mn1-O2 90.18(4) O5-Mn1-O2 105.96(4)O3-Mn1-O1 91.36(3) O4-Mn1-O1 86.97(3)O6-Mn1-O1 94.49(4) O5-Mn1-O1 164.04(4)O2-Mn1-O1 58.11(3)Torsion AnglesS1-C5-C6-S2 38.49(6) S2-C9-C10-S3 150.35(7)169Appendix A. X-Ray DataTable A.26: Selected bond lengths (?) and angles (?) of 118.Bond lengthsC6 C4A 1.459(3) C6 C4B 1.494(10)) S6A C1A 1.729(2)S6A-C4A 1.752(4) S6B-C4B 1.71(3) S6B-C2B 1.73(2)Torsion AnglesC7-C6-C4A-S6A 178.5(3) C5-C6-C4B-S6B 178.8(11)Table A.27: Selected bond lengths (?) and angles (?) of 119.Bond lengthsC4-C7 1.461(2) C1-S1 1.712(2) C4-S1 1.7333(18)C13-C16 1.463(2) C10-S2 1.703(2) C13-S2 1.7295(19)C25-C22 1.463(2) C19-S3 1.733(8) S3-C22 1.703(2)C19B-S3B 1.710(15) S3B-C22 1.675(2)Torsion AnglesS1-C4-C7-C8 -129.59(16) S2-C13-C16-C17 -147.45(15)C26-C25-C22-S3 -153.1(11) C24-C25-C22B-S3B -151.9(13)170Appendix A. X-Ray DataTable A.28: Selected bond lengths (?) and angles (?) of 126.Bond lengthsC2-C4 1.448(17) C4-S1 1.710(13) C7-S1 1.685(15)C9-C11 1.463(17) C11-S2 1.716(12) C14-S2 1.709(12)C16-C18 1.48(2) C16-C18B 1.51(3) C18-S3 1.727(15)C18B-S3B 1.720(18) C21-S3 1.701(15) C21B-S3B 1.701(18)N1-N2 1.351(14) N1-Au3 1.978(10) N2-Au1 2.015(10)N3-N4 1.348(14) N3-Au1 1.982(10) N4-Au2 2.016(11)N5-N6 1.360(13) N5-Au2 2.000(10) N6-Au3 1.990(9)Au1-Au2 3.3817(7) Au1-Au3 3.3454(7) Au2-Au3 3.3045(7)AnglesN2-N1-Au3 121.8(8) N1-N2-Au1 118.2(7)N4-N3-Au1 121.3(8) N3-N4-Au2 119.8(8)N6-N5-Au2 118.3(7) N5-N6-Au3 119.9(7)N3-Au1-N2 177.9(4) N5-Au2-N4 178.3(5)N1-Au3-N6 177.4(5) Au2-Au3-Au1 61.131(15)Torsion AnglesC1-C2-C4-S1 -155.6(12) C8-C9-C11-S2 -145.4(12)C15-C16-C18-S3 -154.0(14) C17-C16-C18B-S3B -152(2)171Appendix A. X-Ray DataTable A.29: Selected bond lengths (?) and angles (?) of 131.Bond lengthsC3-C6 1.46(2) C6-S1 1.704(17) C9-S1 1.72(2)C18-C21 1.42(2) C21-S2 1.733(18) C24-S2 1.730(17)C33-C36 1.45(2) C36-S3 1.75(2) C39-S3 1.728(9)N1-N2 1.357(16) N1-Au1 2.007(10) N2-Au2 2.019(12)N3-N4 1.379(16) N3-Au2 2.020(11) N4-Au3 2.017(12)N5-N6 1.365(17) N5-Au3 2.003(11) N6-Au1 2.011(12)Au1-Au2 3.3700(8) Au2-Au1 3.1091(10) Au1-Au2 3.370(2)Au2-Au3 3.3368(9)AnglesN2-N1-Au1 118.9(9) N1-N2-Au2 121.1(8)N4-N3-Au2 119.3(8) N3-N4-Au3 118.7(9)N6-N5-Au3 121.4(8) N5-N6-Au1 118.9(8)N1-Au1-N6 176.4(6) N2-Au2-N3 175.6(5)N5-Au3-N4 178.3(6) Au3-Au2-Au1 60.670(17)Torsion AnglesC2-C3-C6-S1 -84(2) C17-C18-C21-S2 90.3(19)C34-C33-C36-S3 109(2)172Appendix BPXRD Data5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.1: Experimental (red) and predicted (blue) PXRD patterns of 71.173Appendix B. PXRD Data5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.2: Experimental (red) and predicted (blue) PXRD patterns of 72.10 20 30 400500100015002? (?)Intensity(Countss?1 )Figure B.3: Experimental (red) and predicted (blue) PXRD patterns of 73.174Appendix B. PXRD Data5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.4: Experimental (red) and predicted (blue) PXRD patterns of 74.5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.5: Experimental (red) and predicted (blue) PXRD patterns of 75.175Appendix B. PXRD Data5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.6: Experimental (red) and predicted (blue) PXRD patterns of 76.5 10 15 20 25 300500100015002? (?)Intensity(Countss?1 )Figure B.7: Experimental (red) and predicted (blue) PXRD patterns of 77.176Appendix B. PXRD Data5 10 15 20 25 30 350501001502002503002? (?)Intensity(Countss?1 )Figure B.8: Experimental PXRD pattern of 78.5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.9: Experimental (red) and predicted (blue) PXRD patterns of 79.177Appendix B. PXRD Data5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.10: Experimental (red) and predicted (blue) PXRD patterns of 80.5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.11: Experimental (red) and predicted (blue) PXRD patterns of 81.178Appendix B. PXRD Data5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.12: Experimental (red) and predicted (blue) PXRD patterns of 82.1 0 2 0 3 0 4 001 0 02 0 03 0 04 0 05 0 06 0 02? (?)Intensity(Countss?1 )Figure B.13: Experimental PXRD pattern of 83.179Appendix B. PXRD Data5 10 15 20 25 30 350200040006000800010000120002? (?)Intensity(Countss?1 )Figure B.14: Experimental (red) and predicted (blue) PXRD patterns of 85.10 20 30 400500100015002? (?)Intensity(Countss?1 )Figure B.15: Experimental (red) and predicted (blue) PXRD patterns of 92.180Appendix B. PXRD Data5 10 15 20 25 30 3502004006008002? (?)Intensity(Countss?1 )Figure B.16: Experimental (red) and predicted (blue) PXRD patterns of 93.10 20 30 400500100015002? (?)Intensity(Countss?1 )Figure B.17: Experimental (red) and predicted (blue) PXRD patterns of 94.181Appendix B. PXRD Data5 10 15 20 25 30 350500100015002? (?)Intensity(Countss?1 )Figure B.18: Experimental (red) and predicted (blue) PXRD patterns of 95.10 20 30 400500100015002? (?)Intensity(Countss?1 )Figure B.19: Experimental (red) and predicted (blue) PXRD patterns of 96.182Appendix B. PXRD Data10 20 30 400500100015002? (?)Intensity(Countss?1 )Figure B.20: Experimental (red) and predicted (blue) PXRD patterns of 97.10 20 30 400500100015002? (?)Intensity(Countss?1 )Figure B.21: Experimental (red) and predicted (blue) PXRD patterns of 98.183Appendix B. PXRD Data5 10 15 20 25 30 350500010000150002? (?)Intensity(Countss?1 )Figure B.22: Experimental (red) and predicted (blue) PXRD patterns of 128.184

Cite

Citation Scheme:

        

Citations by CSL (citeproc-js)

Usage Statistics

Share

Embed

Customize your widget with the following options, then copy and paste the code below into the HTML of your page to embed this item in your website.
                        
                            <div id="ubcOpenCollectionsWidgetDisplay">
                            <script id="ubcOpenCollectionsWidget"
                            src="{[{embed.src}]}"
                            data-item="{[{embed.item}]}"
                            data-collection="{[{embed.collection}]}"
                            data-metadata="{[{embed.showMetadata}]}"
                            data-width="{[{embed.width}]}"
                            async >
                            </script>
                            </div>
                        
                    
IIIF logo Our image viewer uses the IIIF 2.0 standard. To load this item in other compatible viewers, use this url:
http://iiif.library.ubc.ca/presentation/dsp.24.1-0165852/manifest

Comment

Related Items