Type of Document Master's Thesis Author Williams, R. Lee Author's Email Address firstname.lastname@example.org URN etd-08212001-145348 Title Ruthenium-Platinum Polypyridyl Complexes: Synthesis and Characterization Degree Master of Science Department Chemistry Advisory Committee
Advisor Name Title Brewer, Karen J. Committee Chair Deck, Paul A. Committee Member Tissue, Brian M. Committee Member Winkel, Brenda S. J. Committee Member Keywords
- bridging ligand
Date of Defense 2001-04-09 Availability restricted AbstractA series of bimetallic (RuII, PtII) complexes were synthesized with the general formula [(tpy)RuCl(BL)PtCl2](PF6) (tpy = 2,2':6',2"-terpyridine and BL = bridging ligand) and their spectroscopic, electrochemical, and DNA binding properties studied. The bridging ligands used in these complexes were 2,3-bis(2'-pyridyl)pyrazine (dpp), 2,3-bis(2'-pyridyl)quinoxaline (dpq) and 2,3-bis(2'-pyridyl)benzoquinoxaline (dpb). These complexes combine light-absorbing RuII-polypyridyl chromophores and a cis-PtCl2 structural motif known to bind DNA. The Ru-bound chloride may be substituted, enabling further modification of the spectroscopic properties. The synthesis of [(tpy)RuCl(BL)PtCl2](PF6) utilizes a building block approach that allows modifications to the series of complexes within the general synthetic scheme. This illustrates the applicability of this scheme to the development of new series of complexes.
The lowest-energy absorption for the three complexes is assigned to a Ru(dp)-to-BL(p*) charge transfer transition. This transition shifts to lower energy as the ligand is varied from dpp to dpq to dpb. The first and second reductions are BL(0/-) and BL(-/2-) based and shift to more positive potentials from dpp to dpq to dpb. The Ru(II/III) redox couple remains at a nearly constant potential for the series. All three compounds show DNA binding when incubated with linearized plasmid DNA. Adduct formation was assessed by agarose gel electrophoresis as a retardation of band migration.
when incubated with linearized plasmid DNA. Adduct formation was assessed by agarose gel electrophoresis as a retardation of band migration.
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