The first example of a working model of the photosynthetic antenna-reaction center complex, constructed via self-assembled supramolecular methodology, is reported. For this, a supramolecular triad is assembled by axially coordinating imidazole-appended fulleropyrrolidine to the zinc center of a covalently linked zinc porphyrin-boron dipyrrin dyad. Selective excitation of the boron dipyrrin moiety in the boron dipyrrin-zinc porphyrin dyad resulted in efficient energy transfer (k(ENT)(singlet) = 9.2 x 10(9) s(-)(1); Phi(ENT)(singlet) = 0.83) creating singlet excited zinc porphyrin. Upon forming the supramolecular triad, the excited zinc porphyrin resulted in efficient electron transfer to the coordinated fullerenes, resulting in a charge-separated state (k(cs)(singlet) = 4.7 x 10(9) s(-)(1); Phi(CS)(singlet) = 0.9). The observed energy transfer followed by electron transfer in the present supramolecular triad mimics the events of natural photosynthesis. Here, the boron dipyrrin acts as antenna chlorophyll that absorbs light energy and transports spatially to the photosynthetic reaction center, while the electron transfer from the excited zinc porphyrin to fullerene mimics the primary events of the reaction center where conversion of the electronic excitation energy to chemical energy in the form of charge separation takes place. The important feature of the present model system is its relative "simplicity" because of the utilized supramolecular approach to mimic rather complex "combined antenna-reaction center" events of photosynthesis.

Supramolecular triads have been constructed by using covalently linked zinc porphyrin−ferrocene(s) dyads, self-assembled via axial coordination to either pyridine- or imidazole-appended fulleropyrrolidine. These triads were characterized by optical absorption, computational, and electrochemical methods. The calculated binding constants (K) revealed stable complexation and suggested the existence of intermolecular interactions between the ferrocene and fullerene entities. Accordingly, the optimized geometry obtained by ab initio B3LYP/3-21G(*) methods revealed closely spaced ferrocene and fullerene entities in the studied triads. Photoinduced charge-separation and charge-recombination processes were examined in the dyads and triads by means of time-resolved transient absorption and fluorescence lifetime measurements. In the case of zinc porphyrin−ferrocene(s) dyads, upon photoexcitation, efficient (ΦCS = 0.98) to moderate (ΦCS = 0.54) amounts of electron transfer from the ferrocene to the singlet excited zinc porphyrin occurred depending upon the nature of the spacer, resulting in the formation of the Fc+−ZnP•- radical pair. Upon formation of the supramolecular triads by axial coordination of fulleropyrrolidines, the initial electron transfer originated either from or to the singlet excited zinc porphyrin, resulting ultimately in the formation of the charge-separated states of Fc+−ZnP:C60 •- with high quantum efficiency. The calculated ratio of k CS/k CR from the kinetic data was found to be ∼100, indicating a moderate amount of charge stabilization in the studied supramolecular triads.

A zinc porphyrin dimer-fullerene supramolecular complex with a large association constant is assembled; efficient intramolecular photoinduced electron transfer from the singlet excited state of zinc porphyrin to the fullerene is observed.