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Peculiar Photoinduced Electron Transfer in Porphyrin-Fullerene Akamptisomers.
Chemistry : a European Journal 2018 December 6
Porphyrin-fullerene dyads are promising candidates for organic photovoltaic devices. Electron transfer (ET) properties of the molecular devices depend significantly on the mutual position of the donor and acceptor. Recently, a new type of molecular isomerism (akamptisomerism) has been discovered. In the present study, we explore how photoinduced ET can be modulated by passing from one akamptisomer to another. To this aim, four akamptisomers of quinoxalinoporphyrin-[60]fullerene complex are selected for the computational study. The most striking finding is that, depending on the isomer, the porphyrin unit in the dyad can act as either electron donor or electron acceptor. Thus, the stereoisomeric diversity allows one to change the direction of ET between the porphyrin and fullerene moieties. To understand the effect of akamptisomerism on the photoinduced ET processes a detailed analysis of initial and final states involved in the ET is performed. The computed rate for charge separation is estimated to be in the region of 1-10 ns-1. The formation of a long-living quinoxalinoporphyrin anion-radical species is predicted.
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