| The study of ruthenium complexes of redox active, non-innocent ligands has long been a pursuit of this research group. In this thesis that work was extended by the investigation of three projects. The first was the investigation of the electronic structure of the solvatochromic compound [Ru(bpy)2 (dadib)]2+, where bpy = 2,2'-bipyridine, and dadib = 3,4-diamino-3',4'-diimino-3 ',4'-dihydrobiphenyl. The dadib ligand has amino groups which are responsible for the pH dependence of the electronic spectrum of this complex, its formation of an adduct with BF3 and its solvatochromism. This complex was investigated with electronic spectroscopy, resonance Raman spectroscopy and electrochemistry. ZINDO molecular orbital and spectroscopic calculations were used to rationalize the solvatochromism.;The second area was the study of the electronic structure of [Ru(NH 3)4(R2-BQDI)]2+/3+, as a function of the metal oxidation state, where R2-BQDI = a 4,5-disubstituted o-benzoquinonediimine ligand and R = H, Cl or OCH3. This involved the synthesis, characterization and isolation of the [Ru(NH 3)4(R2-BQDI)]2+ complexes. The Ru(III) complexes were observed spectroscopically and the R = H species was isolated as a solid. The electronic structure of these complexes were studied by electrochemistry and spectroelectrochemistry, UV-Vis and EPR spectroscopies. ZINDO MO calculations were performed on these complexes in the Ru(II) and Ru(III) oxidation states.;The third project was the study of the symmetric and asymmetric complexes [(Ru(NH3)4)2(catH4.catH 4)]4+ and [Ru(bpy)2(catH 4.catH4)Ru(NH3)4] 4+, where (catH4.catH4) = 3,3 ',4,4''-tetraatminobiphenyl. These complexes were synthesized and characterized in their fully reduced forms. The complexes were chemically oxidized by addition of Ce(IV). The electronic spectra of the 0-, 2- and 4- electron oxidized species were obtained. The electronic structure of these complexes were analyzed by ZINDO MO calculations. |
