Conjugated Porphyrin Dimers: Cooperative Effects and Electronic Communication in Supramolecular Ensembles with C₆₀

Two new conjugated porphyrin-based systems (dimers 3 and 4) endowed with suitable crown ethers have been synthesized as receptors for a fullerene-ammonium salt derivative (1). Association constants in solution have been determined by UV-vis titration experiments in CH₂Cl₂ at room temperature. The designed hosts are able to associate up to two fullerene-based guest molecules and present association constants as high as ∼5 × 10⁸ M^-1. Calculation of the allosteric cooperative factor α for supramolecular complexes [3·1₂] and [4·1₂] showed a negative cooperative effect in both cases. The interactions accounting for the formation of the associates are based, first, on the complementary ammonium-crown ether interaction and, second, on the π-π interactions between the porphyrin rings and the C₆₀ moieties. Theoretical calculations have evidenced a significant decrease of the electron density in the porphyrin dimers 3 and 4 upon complexation of the first C₆₀ molecule, in good agreement with the negative cooperativity found in these systems. This negative effect is partially compensated by the stabilizing C₆₀-C₆₀ interactions that take place in the more stable syn-disposition of [4·1₂].