Electronic energy harvesting multi BODIPY-zinc porphyrin dyads accommodating fullerene as photosynthetic composite of antenna-reaction center

Abstract

Efficient electronic energy transfer (EET) in the newly synthesized dyads comprised of zinc porphyrin covalently linked to one, two or four numbers of boron dipyrrin (BDP) entities is investigated. Both steady-state and time-resolved emission as well as transient absorption studies revealed occurrence of efficient singlet-singlet energy transfer from BDP to zinc porphyrin with the time scale ranging between 28 and 48 ps. A decrease in time constants for energy transfer with increasing the number of BDP units is observed revealing better antenna effect of dyads bearing higher number of boron dipyrrin entities. Further, supramolecular triads to mimic the 'antenna-reaction center' functionality of photosynthetic reaction center have been successfully constructed by coordinating fulleropyrrolidine appended with an imidazole ligand to the zinc porphyrin. The structural integrity of the supramolecular triads was arrived by optical, computational and electrochemical studies. Free energy calculations revealed possibility of photoinduced electron transfer from singlet excited zinc porphyrin to fullerene, and the preliminary transient absorption studies involving pump-probe technique are supportive of occurrence of electron transfer from (1)ZnP* to fullerene in the supramolecular triads.