Date of Graduation

8-2016

Document Type

Thesis

Degree Name

Master of Science in Chemistry (MS)

Degree Level

Graduate

Department

Chemistry & Biochemistry

Advisor/Mentor

Bill Durham

Committee Member

Jingyi Chen

Second Committee Member

Stefan Kilyanek

Keywords

Pure sciences, Ruthenium(II) Polypyridyl Complexes

Abstract

A bridging ligand 5,5’-Bi- 1,10-phenanthroline, diphen, was prepared using dichlorobis(triphenylphosphine)Ni(II), Ni(PPh3)2Cl2 as catalyst with a yield of 40%. Yellow cubic crystals were able to obtain from the good purity product for single crystal analysis. The torsion angle between the planes of the subunit phenanthrolines is about 66 degrees.

A dinuclear ruthenium (II) polypyridyl complex, (phen)2Ru(diphen)Ru(phen)24+, was synthesized by using polymeric ruthenium carbonyl compound as the entry point, diphen as the bridging ligand and 1,10-phenanthroline, phen, as the terminal legand. Brown needlelike crystals were precipitated from acetonitrile that were not suitable for single crystal diffraction.

The photochemistry of the dimer was investigated in regards to the oxidation and reduction of the ruthenium centers through a series of quenching reactions excited by visible light. The analogous monomeric complexes Ru(bpy)32+ and Ru(phen)32+ were used as comparisions. In the photoinduced oxidation with peroxydisulfate, S2O82-, the dimer showed a higher Stern-Volmer quenching constant kq than Ru(phen)32+. The dimer showed faster laser flash photolysis transients than Ru(bpy)32+. In the photoinduced reduction with ascorbate, no significant difference between the dimer and Ru(phen)32+.

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