Synthesis of Uniquely Functionalised Tetrabenzotriazaporphyrins

Tetrabenzotriazaporphyrins (TBTAPs) are hybrid structures that lie between the omnipresent phthalocyanines and tetrabenzoporphyrins. These classes of materials are famous for their remarkable electronic and physical properties which result from the extensive delocalization of the π-electrons in their inner core. TBTAPs were found to share similar properties with these macrocyclic materials, however, the difficulties in their synthesis and purification made the interest in them rare and scarce unlike Pc and TBP. A brief review of the number of synthetic methods reported for their synthesis is described in Chapter 1, in addition to a summary of their distinctive properties and applications. The synthesis of substituted derivatives is often driven by the desire to exploit and improve their performance. The research group at UEA has reported a straightforward, high‐yielding synthesis of meso‐aryl tetrabenzotriazaporphyrins, thus extending the access to these hybrids. Developing this synthetic procedure, from phthalonitrile and aminoisoindoline, the work in this thesis entails the synthesis of a range of novel and unique peripheral substituted MgTBTAPs bearing aryl substituent at their mesoposition. The synthesis of the new compounds, which is described in Chapter 2, is based on employing aminoisoindoline and phthalonitrile derivatives to functionalize the benzo-units on the macrocycle and explanation of the conjugated system has been also described. In order to prepare these complexes, we have prepared a new series of substituted bromobenzamidine, aminoisoindoline and aza-dipyrromethene derivatives. Within this study a new synthesis has been uncovered whereby, for the first time, meso-aryl ABBA substituted TBTAPs are conveniently prepared