Synthesis and characterization of late transition metal oligothiophene complexes for light harvesting applications
department or school: Science, Faculty of
department or school: Chemistry, Department of
data provider: DSpace
degree campus: UBCV
creator: Moore, Stephanie Amber
issued: 2014-06-30T07:00:00Z
issued: 2012
related degree: Doctor of Philosophy - PhD
degree grantor: University of British Columbia
description: The synthesis and characterization of late transition metal complexes combined with the β-substituted 3ʹ-(diphenylphosphino)-2,2ʹ:5ʹ,2ʺ-terthiophene (PT₃) to yield metal-oligothiophene hybrid complexes are reported. These new complexes (shown on the following page) were studied with absorption, emission, and transient absorption spectroscopies, electrochemistry and X-ray crystallography. Ru(II) and Os(II) bis(diimine) complexes (52-53 and 54-55, respectively) containing PT₃ in two different coordination modes (PS and PC bound) are reported. The binding mode is shown to affect the structural, photophysical and electronic properties of the complexes. Transient absorption spectra and lifetimes were obtained for all the complexes, and support a PT₃ ligand-based lowest excited state in the case of the PS bound complexes, and a charge separated lowest excited state in the PC bound complexes. The DFT calculations and experimental results agree well. Cyclometalated iridium (III) complexes (58-63) were synthesized using microwave irradiation. In addition to the PS and PC coordination modes observed in the group 8 complexes, a third, monodentate, coordination mode was observed (P). The lowest energy absorption band and emission band shift based on the PT₃ coordination mode. The nature of the excited state lifetimes did not change with coordination mode; all were assigned as a PT3 ligand-based excited state, however, the excited state lifetimes are influenced by the coordination mode. Heteroleptic Cu(I) complexes (75-76) were synthesized and yielded three and four coordinate complexes. The electrochemical and photophysical properties of these complexes vary with solvent. Minor changes are observed in the absorption spectra when obtained in different solvents, but interesting differences are observed in the electrochemical reversibility, excited state lifetimes, and profiles of the emission and transient absorption spectra.
aggregated CHO: https://circle.library.ubc.ca/rest/handle/2429/42482
note: SYNTHESIS AND CHARACTERIZATION OF LATE TRANSITION METAL OLIGOTHIOPHENE COMPLEXES FOR LIGHT HARVESTING APPLICATIONS by Stephanie Amber Moore B.Sc. (Hons.), St. Francis Xavier University, 2006 A THESIS SUBMITTED IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in The Faculty of Graduate Studies (CHEMISTRY) THE UNIVERSITY OF BRITISH COLUMBIA (Vancouver) June 2012 © Stephanie Amber Moore, 2012. ii ABSTRACT The synthesis and characterization of late transition metal complexes combined with the β-substituted 3ʹ-(diphenylphosphino)-2,2ʹ:5ʹ,2ʺ-terthiophene (PT3) to yield metal-oligothiophene hybrid complexes are reported. These new complexes (shown on the following page) were studied with absorption, emission, and transient absorption spectroscopies, electrochemistry and X-ray crystallography. Ru(II) and Os(II) bis(diimine) complexes (52-53 and 54-55, respectively) containing PT3 in two different coordination modes (PS and PC bound) are reported. The binding mode is shown to affect the structural, photophysical and electronic properties of the complexes. Transient absorption spectra and lifetimes were obtained for all the complexes, and support a PT3 ligand-based lowest excited state in the case of the PS bound complexes, and a charge separated lowest excited state in the PC bound complexes. The DFT calculations and experimental results agree well. Cyclometalated iridium (III) complexes (58-63) were synthesized using microwave irradiation. In addition to the PS and PC coordination modes observed in the group 8 complexes, a third, monodentate, coordination mode was observed (P). The lowest energy absorption band and emission band shift based on the PT3 coordination mode. The nature of the excited state lifetimes did not change with coordination mode; all were assigned as a PT3 ligand-based excited state, however, the excited state lifetimes are influenced by the coordination mode. Heteroleptic Cu(I) complexes (75-76) were synthesized and yiel…
has type: Thesis/Dissertation
date issued: 2012-11
is shown at: 10.14288/1.0062419
language: eng
degree discipline: Chemistry
provider: Vancouver : University of British Columbia Library
publisher: University of British Columbia
rights: Attribution-NonCommercial-NoDerivatives 4.0 International
rights URI: http://creativecommons.org/licenses/by-nc-nd/4.0/
scholar level: Graduate
type: Text
identifier URI: http://hdl.handle.net/2429/42482