Synthetic studies towards multichromophore arrays
The overall aim of this project was to investigate strategies for linking macrocyclic chromophores to form arrays. Firstly the aim was to link a porphyrin to a triphenylene through phenyl alkynes. Interestingly, this study discovered a mesogenic dibromtetramethoxy triphenylene – the least heavily substituted triphenylene liquid crystal reported to date. The results of this investigation, however, show that, in general, it was challenging to force the reaction between porphyrin and triphenylene components to form acetylene links. Dimerization of the acetylene components was observed as the predominant reaction in all cases. However, it was possible to isolate a porphyrin-triphenylene dyad structure. The second aim of this study was to investigate the synthesis of novel chromophore dyads and triads 102, 104 and 134 which are based on porphyrin and tetrabenzotriazaporphyrin (TBTAP) components. The first aim was to synthesise porphyrin–phenyl-TBTAP 102. A precursor porphyrin bearing aminoisoindoline functionality was successfully prepared. However, it could not be converted to either the porphyrin–phenyl-TBTAP 102 dyad or porphyrin-azaBODIPY-porphyrin triad 134. On the other hand, the suggested strategy towards the synthesis of porphyrin-TBTAP dyads linked through flexible chains (104) remains promising. Magnesium TBTAB-OH 135 was synthesised as one important reactant. However, the unfortunate choice of bromododecyloxyporphyrin 141, meant the synthesis of the desired dyad could not be achieved within this project because it could not be separated from excess dibromododecane. However, simple modification of the strategy (e.g using bromododecanol) will allow the compounds to be prepared in the future.
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