A Supramolecular Photosynthetic Model Made of a Multi-Porphyrinic Array Constructed Around a C60 Core and a C60-Imidazole Derivative

The photophysical properties of a supramolecular fullerene-porphyrin ensemble resulting from the self-assembly of a pyrrolidinofullerene-imidazole derivative (F1) with a multi-metalloporphyrin array constructed around a hexa-substituted fullerene core (F(ZnP)₁₂) have been investigated. The fullerene hexa-adduct core of the host system does not play any active role in the cascade of photoinduced events of the supramolecular ensemble, indeed no intercomponent photoinduced processes could be observed in host F(ZnP)₁₂. In contrast, upon axial coordination with the mono-substituted fullerene guest F1, a quantitative quenching of the fluorescence signal of the metalloporphyrins was observed for the supramolecular complex [F(ZnP)₁₂ (F1)_n] both in polar and non polar solvents. In toluene, the supramolecular ensemble exhibits a charge transfer emission centered around 930 nm suggesting the occurrence of intramolecular face-to-face interactions of F1 with neighboring metalloporphyrin moieties within the self-assembled photoactive array. This mechanism is supported by the fact that a one  order of magnitude increase in the binding constant was observed for the supramolecular complex [F(ZnP)₁₂ (F1)_n] when compared to a reference system lacking the pyrrolidino-fullerene unit. In benzonitrile, a long-lived charge separated state (τ = 0.3 μs) has been detected for the supramolecular adduct.

References
K. Yoosaf, J. Iehl, I. Nierengarten, M. Hmadeh, A.-M. Albrecht-Gary, J.-F. Nierengarten, N. Armaroli, Chem. Eur. J., 2014, in press