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.
| Identifer | oai:union.ndltd.org:ADTP/217755 |
| Date | January 2007 |
| Creators | Walsh, Penelope Jane, n/a |
| Publisher | University of Otago. Department of Chemistry |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | http://policy01.otago.ac.nz/policies/FMPro?-db=policies.fm&-format=viewpolicy.html&-lay=viewpolicy&-sortfield=Title&Type=Academic&-recid=33025&-find), Copyright Penelope Jane Walsh |
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