This thesis presents a spectroscopic and computational study of a variety of substituted oligothiophenes. The purpose of this study was to elucidate the structural properties of their neutral, oxidised and excited states. This was accomplished using a number of spectroscopic methods, including electronic absorption, resonance Raman and fluorescence spectroscopy. Analysis of the data provided by these methods was aided by the application of density functional theory (DFT) to the neutral and charged species, allowing conclusions regarding bond length changes and molecular orbitals to be drawn. Advancing the understanding of the structural properties of conductive materials such as oligothiophenes is important due to their potential application in plastic electronic devices (organic solar cells, field effect transistors and light emitting diodes, for instance) and the need to clarify the charge transport mechanism.
The compounds examined in this thesis are primarily based on 3� styryl-substituted terthiophene. Substituted derivatives of this molecule include those with groups on the para position of the phenyl ring or methyl α,α� end caps. Larger ethenyl-aryl groups were also investigated, as were analogous thiophenes and sexithiophenes. Indeed, the 3�-substituted sexithiophenes formed an integral part of this investigation since they rapidly form in the head-to-head orientation from the oxidation and consequent [sigma]-dimerisation of the substituted terthiophenes.
DFT calculations on the sexithiophene charged species have indicated the presence of a full polaronic or bipolaronic structural defect in the centre of the thiophene backbone, as defined by the reversal of the CC bond length alternation to create a domain of quinoidal bond sequence. However, the structural defect of the styryl sexithiophenes is more strongly localised than that observed for unsubstituted sexithiophene; indeed, the charged defect appears to be confined by the positions of the styryl substituents. This defect confinement along the thiophene backbone is particularly apparent in the styryl sexithiophene dications.
Electronic absorption and resonance Raman spectroscopy have been applied to the oxidation products of the styryl terthiophenes. Only sexithiophene charged species are observed when the α termini are unsubstituted; these include sexithiophene radical cations, [pi]-dimers (a stabilising face-to-face interaction between two radical cations) and dications. The resonance Raman spectra of these charged species are characterised by a very intense symmetrical CC stretching mode of the thiophene inter-ring bonds, which is also evident in the theoretical spectra. The extensive differences between the styryl and unsubstituted sexithiophene dication Raman spectra have been attributed to defect confinement: the strongest Raman band of the unsubstituted sexithiophene dication is due to a vibrational mode localised over the entire sexithiophene backbone while that of the styryl sexithiophenes is localised over the central two thiophene rings - the same area occupied by the confined defect.
A combined steady-state and picosecond time-resolved emission study on the styryl terthiophenes revealed that by judicious choice of the para R group in styryl terthiophenes it is possible to tune the nature of the first excited singlet state from [pi],[pi]* to charge transfer character. Charge transfer states may offer possible strategies for solar cells in which charge separation is a key step.
| Identifer | oai:union.ndltd.org:ADTP/217563 |
| Date | January 2007 |
| Creators | Clarke, Tracey Michelle, 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 Tracey Michelle Clarke |
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