Photoinduced Electron Transfer in “Two-Point” Bound Supramolecular Triads Composed of N,N-Dimethylaminophenyl-Fullerene-Pyridine Coordinated to Zinc Porphyrin

Abstract

Stable with defined distance and orientation, self-assembled supramolecular triads composed of N,Ndimethylaminophenylfullerene-pyridine bound to zinc porphyrins by a newly developed “two-point” binding strategy are reported. For this, zinc porphyrin was derivatized to bear “hydrogen-bonding” functionalities, carboxylic acid or amide groups, and C60 was functionalized to bear a ligating group, pyridine, and a second electron donor, N,N-dimethylaminophenyl group. The supramolecular triads formed by self-assembly of the zinc porphyrin and fullerene derivatives via the two-point binding method were characterized by spectroscopic and electrochemical techniques and were modeled by using ab initio computational methods. Evidence for axial coordination of the pyridine entity to the zinc metal center and H-bonding between the pyrrolidine ring nitrogen and the pendant carboxylic acid or amide groups was obtained. In the supramolecular triads, the second electron donor, N,N-dimethylaminophenyl, promotes efficient charge separation upon excitation of the zinc porphyrin to yield the radical ion pairs. The radical ion pairs thus generated undergo slow charge recombination to yield relatively long-lived (30-40 ns) charge-separated states.