Structure-Photoproperties Relationship Investigation of the Singlet Oxygen Formation in Porphyrin-Fullerene Dyads

Abstract

A systematic structure-photoproperties relationship study of the interactions of porphyrin-fullerene dyads with molecular oxygen was conducted on a set of three porphyrin-fullerene dyads, as this approach of related applications - oxygen sensitivity and photo-induced singlet oxygen generation - of such dyads remained to be endeavoured. To promote energy transfers between the porphyrin and fullerene units and limit undesired charge separation, a particular attention was devoted to the choice of the solvents for the photoproperties determination. Toluene, in which in addition the compounds investigated are not aggregated, was selected accordingly. The molecular orbital levels and energy gaps of the dyads were determined by electrochemistry and theoretical calculations. Their ground state absorption, steady-state fluorescence-based oxygen sensitivity and photo-induced singlet oxygen generation were determined. The dyads were designed to benefit from a facilitated synthetic porphyrin-fullerene coupling thanks to an easy access to formyl-functionalized porphyrins. The effect of two structural parameters was investigated: the presence of electron-donating hexyloxy chains at the para position of the meso-phenyl, and the presence of a phenylacetylene spacer. This latest factor appeared to have the most predominant effect on all these properties.