Understanding Charge-Transfer Characteristics in Crystalline Nanosheets of Fullerene/(Metallo)porphyrin Cocrystals.

Cocrystals in the form of crystalline nanosheets comprised of C and (metallo)porphyrins were prepared by using the liquid-liquid interfacial precipitation (LLIP) method where full control over the morphologies in the C/(metallo)porphyrins nanosheets has been accomplished by changing the solvent and the relative molar ratio of fullerene to (metallo)porphyrin. Importantly, the synergy of integrating C and (metallo)porphyrins as electron acceptors and donors, respectively, into nanosheets is substantiated in the form of a near-infrared charge-transfer absorption. The presence of the latter, as reflection of ground-state electron donor-acceptor interactions in the nanosheets, in which a sizable redistribution of charge density from the electron-donating (metallo)porphyrins to the electron-accepting C occurs, leads to a quantitative quenching of the localized (metallo)porphyrin fluorescence. Going beyond the ground-state characterization, excited-state electron donor-acceptor interactions are the preclusion to a full charge transfer featuring formation of a radical ion pair state, that is, the one-electron reduced fullerene and the one-electron oxidized (metallo)porphyrin.