A new approach for studying thermal phase separation in sodium borosilicate glasses using Mn('2+) as a luminescent probe is investigated. Seventy-one samples of glasses activated by Mn('2+) inside and around the Na(,2)O(.)B(,2)O(,3)(.)SiO(,2) miscibility gaps were prepared. These samples were then phase separated by dry thermal treatment. / It is shown that on addition of MnO, the ternary Na(,2)O(.)B(,2)O(,3)(.)SiO(,2) system behaved like other quaternary systems of the type X(,2)O(.)MO(.)B(,2)O(,3)(.)SiO(,2) (X = Na, K; M = Mg, Ca, Ba, Zn). Scanning electron microscopy and X-ray microanalysis demonstrated that manganese concentrates preferentially in the boron-rich phase. This analysis, in conjunction with a comparison of Mn('2+) emission spectra of unheated and heat-treated glasses shows that the glasses are submicroscopically phase separated when prepared. The decay-time analysis of Mn('2+) luminescence indicates that the low energy emission band arises from Mn('2+) in the boron-rich phase while the high energy emission is due to Mn('2+) in the silica-rich phase. The difference in the crystal field parameters obtained from the excitation spectra of the two emission bands shows that the high energy emission band is from Mn('2+) in tetrahedral sites while the low energy emission band is from Mn('2+) in an octahedral environment.

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.

Currently, very little information is available for an in-depth understanding of the molecular binding interactions with molecularly imprinted polymers (MIPs). To address this issue MIPs that have high binding affinities for their template compounds were made so that the nature of these interactions could be elucidated using spectroscopic techniques. 12 functional MIPs were prepared using a series of azobenzene and anthracenyl derivatives as the templates. Affinities of these MIPs for the corresponding templates and analogues were determined by performing batch and competitive binding tests. It was found that extensively conjugated compounds that contain at least two OH groups, an electron-withdrawing substituent and have limited conformational freedom were effective templates. The most efficient MIP, M34, was prepared with 4-[(4-nitrophenyl)azo]-1,2-benzenediol (12). M34 exhibited high affinities for azobenzene derivatives of catechol, and bound those that did not contain non electron-withdrawing substituents more specifically. M34 did not lose affinity for 12 in the presence of analogues, and vice versa, in competitive binding tests. These observations suggested a distribution of different binding sites on M34. M34 bound substrates rapidly, which was attributed to its highly porous polymer matrix giving ready access to binding sites. Formation of the porous matrix was facilitated by the use of DMF as the porogen in the preparation of M34. DMF is not a conventional choice of porogen because use of such highly polar H-bonding solvents is thought to disrupt complexation between template and polymer precursors, which is required for the formation of binding sites. Significant changes in the wavenumbers and the intensities of absorption bands assigned to the catechol substructure of 12 were observed in the FT-Raman spectra of 12 bound to M34. These findings suggested that the catechol substructure was responsible for interactions of 12 with M34 that are critical to rebinding and imprinting. In-situ analyses of dithranol (8) being removed from and bound to its MIP, M23, were performed using ATR-IR spectroscopy. Only one band, assigned to the aromatic substructure of 8, was not obstructed by solvent bands in the spectra of unwashed M23 and washed M23 that was treated with the rebinding solution. The wavenumbers of the corresponding bands in the two spectra were significantly different. This observation suggested that there were differences in the vibrational characteristics of 8 bound to M23 under the two conditions. Evidence was found for H-bonding between OH groups of 8 and C=O group of methacrylic acid using transmission FT-IR spectroscopy. However, no evidence was found that showed significant interactions between 12 and 2-vinylpyridine. Methacrylic acid and 2-vinylpyridine were used as the functional monomers in the preparations of M23 and M34. The FT-IR spectra of mixtures of 12 and 4-vinylpyridine showed three new bands assigned to H-bonded OH stretches. These observations indicated that 4-vinylpyridine H-bonds with 12, and would be a more effective functional monomer than 2-vinylpyridine in the preparation of the MIPs for 12. Titration of 12 with 2-vinylpyridine was analysed by �H NMR spectroscopy. Only small changes to the signals of the corresponding compounds were observed. This lack of change was attributed to the use of d₇DMF, which would compete against 2-vinylpyridine for H-bonding interactions. The findings made using ATR-IR spectroscopy and FT-Raman were novel because previously reported data on bound templates obtained using the corresponding techniques did not show changes in the vibrational characteristics of templates as they bind to MIPs. This investigation has shown that rebinding and spectroscopic studies can provide information about the nature of the binding interactions in MIPs.

This thesis reports the spectroscopic and computational studies of two classes of compounds, which have applications in new optoelectronic materials technology. Substituted ligands of dipyrido-[3,2a:2�,3�c]phenazine (dppz), and their Cu(I), Re(I) and Ru(II) complexes have utility in organic electroluminescent devices. A series of Zn(II) tetraphenylporphyrins with conjugated functional groups at the β-position have been used with success in liquid heterojunction dye-sensitized solar cells. The vibrational spectra and optoelectronic properties of the two classes were investigated using Raman, resonance Raman and transient resonance Raman spectroscopy, in conjunction with density functional theory methods. Density functional theory frequency calculations were used to aid vibrational mode assignments for the dppz compounds, and show close agreement with the experimental non-resonance Raman spectra. The enhancement of modes which are localized on differing sections of the ligand was identified. The nature of the absorbing chromophores for the dppz ligands and complexes was established using resonance Raman spectroscopy in concert with vibrational assignments from calculations. Transient resonance Raman spectra of the ligands provided spectral signatures for the triplet ligand-centred state; these features were observed in the TR� spectra of the metal complexes, along with other features attributable to MLCT states. Electroluminescent devices were fabricated using the dppz ligands and complexes as emissive dopants, and their properties investigated. The optoelectronic behaviour of the devices was found to be influenced by the mechanism of exciton formation on the dopant. The device properties were also dependent on the dopant concentration, the concentrations of other components and the driving voltage. The electronic structure of the porphyrin compounds was investigated using time-dependent density functional theory methods. Comparison of calculated optical transitions with experimental data shows that the calculations predict trends in the optical absorption spectra with change of functional group and with increase in conjugation chain length. The calculations suggest that the electron-withdrawing substituent decreases the configuration interaction effect by breaking the degeneracy of the two lowest unoccupied MOs, and other configuration interaction effects come into play involving other frontier MOs. Interrupting the conjugation of the functional group is shown to mitigate the breakdown of the configuration interaction. The perturbation of the normal electronic structure of the porphyrin by the substituent was also investigated using resonance Raman spectroscopy. Vibrational analysis identified bands due to the substituent, implying coupling between the porphyrin and substituent chromophores. Changes in frequency of porphyrin core modes due to the differing substituents and different metal centres were reproduced by density functional theory calculations. This project has allowed the spectroscopic investigation of the active optical states in a number of polypyridyl and porphyrin compounds, and determined the efficacy of DFT and TDDFT calculations to predict the properties of these compounds.

Thesis (Ph. D.)--Georgia State University, 2006. / Title from file title page. Gabor Patonay, committee chair; Zhen Huang, Alfons Baumstark, committee members. Electronic text (236 p. : ill. (some col.)) : digital, PDF file. Description based on contents viewed Jan. 28, 2008. Includes bibliographical references.

Thesis (Ph. D.)--University of Washington, 1988. / Vita. Bibliography: leaves [271]-273.

Thesis (Ph.D.)--McMaster University (Canada), 1993. / Source: Dissertation Abstracts International, Volume: 54-12, Section: B, page: 6270. Adviser: M. S. Patterson.

Thesis (Ph.D.)--McMaster University (Canada), 1988. / Source: Dissertation Abstracts International, Volume: 62-13, Section: A, page: 0000.

Thesis (Ph. D.)--University of Adelaide, Dept. of Biochemistry, 1992. / Cover title: Novel approaches to protein purification and analysis: counter-current electrophoretic filtering: spectral enhancement. Spine title: Protein purification and analysis. Includes bibliographical references.

Thesis (Ph.D.) -- University of Adelaide, Dept. of Physics and Mathematical Physics, 2002. / "October 2002" Bibliography: p. 129-136.