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UBC Theses and Dissertations

Ruthenium and palladium halide complexes containing hemilabile ligands for luminescent chemosensing Matkovich, Kristin M.


The effect of the halide ligand on the fluorescence lifetime of a series of Ru(II) complexes, tcc-RuX₂(POC4Pyr-P,O)₂ (X = Cl (3), Br (4), I (5)) containing the hemilabile phosphine ether ligand 4-{2-(diphenylphosphino)phenoxy}butylpyrene (POC4Pyr (1)), is reported. The synthesis and characterization of both the ligand, POC4Pyr (1), and ligand oxide, P(=O)OC4Pyr (2), and the solid-state structure of 1 are also presented. New complexes based on a similar framework incorporating phosphine pyrenyl imine and phosphine pyrenyl amine ligands and a palladium metal center, PdCl₂(PNPyr-P,N) (14) (PNPyr = 2-diphenylphosphino-N-(1-pyrenyl)benzylidineimine (12)) and PdCl2(PNHPyr-P,N) (15) (PNHPyr = 2-diphenylphosphino-N-(1-pyrenyl)benzylidineamine (13)), are presented . The UV-vis, steady-state fluorescence, and solid state structures of 14 and 15 are presented. The synthesis and characterization, as well as the solid state structures of both ligands, 12 and 13, are also presented. Preliminary steady-state fluorescence experiments provide promising results for a potential “OFF-ON” or “ON-OFF” chemosensor. However, initial reactivity of the palladium complexes with carbon monoxide and sulfur dioxide were unsuccessful; further experiments are needed to optimize the reactivity of these complexes.

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