Stabilization of Charge-Separated States in Phthalocyanine−Fullerene Ensembles through Supramolecular Donor−Acceptor Interactions

A novel ZnPc−C60 dyad (3), in which two photoactive units are brought together by a phenylenevinylene spacer has been synthesized. The synthetic strategy en route toward 3 involves a Heck reaction to attach 4-vinylbenzaldehyde to a monoiodophthalocyanine precursor, followed by standard cycloaddition of azomethine ylides (generated from the formylPc derivative and N-methylglycine) to one of the double bonds of C60. Electrochemical studies reveal that in 3 the ZnPc is about 39 mV more difficult to oxidize than in the corresponding ZnPc reference, which points to appreciable electronic communication between ZnPc and C60 in the ground state. In the excited state, photoexcitation leads to the formation of a charge-separated ZnPc•+−C60 •- state, for which a lifetime of 130 ns was determined in THF. Hetero-association between complementary Pcs (1 and 2 or 3 and 2), which carry different peripheral functionalities (i.e., either electron-donating alkoxy groups or electron-deficient alkylsulfonyl chains) was assessed by different techniques. They provided evidence for donor−acceptor 1:1 complex formation with a stability constant of ca. 105 M-1 in CHCl3. Interestingly, hetero-association of ZnPc−C60 dyad 3 with an electron-deficient PdPc (2) allowed the construction of supramolecular triads, in which a substantial stabilization of the radical pair is seen relative to that of the covalently linked dyad ZnPc−C60 (3).