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.
Two types of structurally well-defined, self-assembled zinc porphyrin-fullerene conjugates were formed by "two-point" binding strategies to probe the effect of axial ligation or pi-pi-type interactions on the photochemical charge stabilization in the supramolecular dyads. To achieve this, meso-tetraphenylporphyrin was functionalized to possess one or four [18]crown-6 moieties at different locations on the porphyrin macrocycle while fullerene was functionalized to possess an alkyl ammonium cation, and a pyridine or phenyl entities. As a result of the crown ether-ammonium cation complexation, and zinc-pyridine coordination or pi-pi-type interactions, stable zinc porphyrin-fullerene conjugates with defined distance and orientation were formed. Evidence for the zinc-pyridine complexation or pi-pi-type interactions was obtained from the spectral and computational studies. Steady-state and time-resolved emission studies revealed efficient quenching of the zinc-porphyrin singlet excited state in these dyads, and the measured rates of charge separation, k(CS) were found to be slightly better in the case of the dyads held by axial coordination and crown ether-cation complexation. Nanosecond transient absorption studies provided evidence for the electron transfer reactions, and these studies also revealed charge stabilization in these dyads. The lifetimes of the radical ion pairs were found to depend upon the type of porphyrins utilized to form the dyads, that is, porphyrin possessing the crown ether moiety at the ortho position of one of the phenyl rings yielded prolonged charge stabilized states. Addition of pyridine to the supramolecular dyads eliminated the zinc-pyridine coordination or pi-pi-type interactions of the "two-point" bound systems due to the formation of a new zinc-pyridine axial bond thus giving a unique opportunity to probe the effect of axial coordination or pi-pi interactions on k(CS) and k(CR). Under these conditions, the measured electron transfer rates revealed faster k(CS) and slower k(CR) as compared to those obtained in the absence of added pyridine. The evaluated lifetimes of the radical ion-pairs were found to be hundreds of nanoseconds and were longer in the presence of pyridine.
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.
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