Characterisation and screening of novel aromatic thin-film materials

Abstract

The electropolymerisation of a range of indole derivatives results in the formation of redox active films. These redox films have been observed to be highly luminescent. Earlier studies have investigated electrochemical and photophysical properties, for potential applications such as fast response potentiometric sensors or novel materials for light emitting devices. The work in this thesis extends this approach to electrochemical and computational studies of a range of novel redox-active aromatic systems. This work has exploited the continuing increase of computing power, employing powerful quantum computational models to complement and augment electrochemical methods. Density Functional Theory has been used to show that prediction of oxidation potentials in good agreement with experimental values is achievable for a wide range of aromatic systems. Calculation of the electron spin density of the radical cations has also helped to elucidate the likely coupling locations for the formation of electroactive layers. It is observed that the nature of substituents and additional hetero groups to the aromatic systems can have a profound effect on electron spin density distributions. The redox-active species formed from indole dimers and 5-methylindolocarbazole have also been characterised. The species formed from electropolymerisation of 5- methylindolocarbazole has been found to be a mixture of three isomers of a 5- methylindolocarbazole dimer. Full characterisation of the product of the electropolymerisation of indole dimers was not possible; fluorescence work however suggests this to be a species with a greater degree of conjugation than either indole dimers or trimers. It is thought likely that this product is either a tetramer or longer chain polymer. This work demonstrates the applicability of a combination of computational and electrochemical methods to the characterisation of novel heteroaromatic systems.