Porphyrin arrays for FET devices
Field effect transistors (FETs) are a key component of modern electronic devices. They require a semiconducting material that is traditionally made from doped silicon. Recently however it has been shown that porphyrin systems can be used in the same capacity. This thesis therefore describes the investigation of new methods of porphyrin functionalization to synthesise 1,4,5,8-tetraazaanthracene-bridged porphyrin arrays, and their application to the synthesis of extended arrays for use in FETs. The 1,4,5,8- tetraazaanthracene bridge is synthesised through the condensation of a porphyrin alpha-dione with 1,2,4,5-tetraaminobenzene. Accordingly, the synthesis of an extended array requires a porphyrin tetra-one monomer unit. Two methods for the synthesis of porphyrin tetra-ones have been investigated. The first approach attempts to adapt Knudsen's hydroxylation of an aryl halide by sodium benzaldoximate to a porphyrin system. Initial regiospecific halogenation of a porphyrin has been successfully achieved. However when hydroxylation was attempted, partial dehalogenation of the substrate was observed; and when applied to the synthesis of the porphyrin tetra-one the methodology failed. The second approach involves the allylic oxidation of a chlorin (a reduced porphyrin) on silica. The transformation's mechanism has been thoroughly investigated and it has been successfully applied to the synthesis of a porphyrin tetra-one. This methodology has then been applied to the synthesis of extended porphyrin arrays. A sample incorporating 12 porphyrin units has been successfully constructed. It has been characterised by NMR, MALDI, GPC and UV-VIS spectroscopy. By comparison with previous results it has been concluded that the aromatic system- which spans 181 Ǻngstroms from end to end- can be described as a series of weakly interacting chromophores, in agreement with theoretical predictions made by Hush. In addition a medium-scale synthesis of an array incorporating four porphyrins has been achieved so that it may now be tested as the semiconducting material in a FET.