This thesis reports the spectroscopic and computational studies of a number of Cu(I), Re(I) and Ru(II) complexes of polypyridyl ligands. The ligands considered in this study were 1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, 3,4,7,8-tetramethyl-1,10-phenanthroline, dibenzo[b,j][1,10]phenanthroline, dipyrido[2,3-a:3�,2�-c]phenazine, dipyrido[2,3-a:3�,2�-c]-6,7-dichlorophenazine and dipyrido[2,3-a:3�,2�-c]-6,7-dimethylphenazine. Density functional theory calculations were carried out on the polypyridyl ligands. Validation of the calculations was carried out by comparison of the predicted values to observables. The structures were compared to previously published X-ray crystal data. Calculated bond lengths were typically calculated to be within 0.02 Å of those in the crystal structure. The calculated vibrational spectra were compared to measured IR and Raman spectra. The correspondence between calculated and measured frequencies was quantified using the mean absolute deviation between the two sets of frequencies. This was typically found to be less than 10 cm⁻�. The robustness of the calculation was further tested by calculations on perdeuterated analogues of some of the ligands. The calculations were extended to metal moieties and validated as for the ligands. Resonance Raman and infrared spectra of the reduced states of some Re(I) complexes are reported. The structure and spectra have been modelled by considering the radical anion of the polypyridyl ligand and the reduced state of the complex. There is improvement in the mean absolute deviation, between calculated and observed frequencies, upon incorporation of the metal moiety into the calculation. Spectra are successfully modelled confirming the validity of the modelled structures. The resonance Raman and infrared spectra of the metal-to-ligand charge transfer excited states of some Cu(I), Re(I) and Ru(II) complexes are reported. Density functional theory calculations on the lowest energy triplet states aided in the spectral assignment of bands. Cu(I) complexes were successfully modelled with mean absolute deviations, between calculated and observed frequencies, of less than 10 cm⁻�. The spectra of the Re(I) and Ru(II) complexes were less successfully modelled. Incorporation of the Ru(II) centre into the calculation of the vibrational frequencies of dipyrido[2,3-a:3�,2�-c]phenazine complexes offers no improvement over modelling the radical anion of this polypyridyl ligand. The excited state lifetimes of a number of polypyridyl complexes have been reported. The changes in lifetimes of similar complexes were found to be consistent with the energy gap law or changes in the conjugation of the involved polypyridyl ligand. This project has allowed the excited state structures of a number of polypyridyl complexes to be determined using vibrational spectroscopy to validate density functional theory calculations. This has provided a study strategy that may be applied to other metal polypyridyl complexes.

Typescript (photocopy) / x, 110 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1983

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Graduation date: 2000

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2007. / Includes bibliographical references. Also available in electronic version.

Thesis (M.A.)--University of North Carolina at Wilmington, 2006. / Includes bibliographical references (leaves: 96-97)

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title from title frame. Also available in printed format.

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Thesis (M.S.)--University of Delaware, 2006. / Principal faculty advisor: Thomas P. Beebe, Jr., Dept. of Chemistry & Biochemistry. Includes bibliographical references.

The development of a palladium-catalyzed intramolecular carboesterification of unactivated olefins is described. Olefin difunctionalization is a powerful tool for adding complexity to a molecule, and this formal [3+2] cycloaddition generates highly functionalized fused ring systems. Initially discovered by Dr. Yang Li in our group, it was found that when propiolic acids with a pendant terminal olefin were treated with 1 mol % Pd(MeCN)2Cl2, 3 equivalents of copper (II) chloride, and 3 equivalents of lithium chloride in acetonitrile at 50 °C, cyclization occurred in up to 90% yield. The optimization of this reaction and the extension to propiolamides and propargyl alcohols is described in this thesis. A mechanism involving a novel palladium-carboxylate species is proposed. Preliminary investigations into the synthesis of chiral sulfoxide pincer ligands are also described. The nucleophilic aromatic substitution of 1,3-dibromobenzene and 2,6-dichloropyridine with various thiols, followed by oxidation of the sulfides to sulfoxides is investigated as a route to the desired proligands.