Excited-State Photodynamics of Perylene−Porphyrin Dyads. 5. Tuning Light-Harvesting Characteristics via Perylene Substituents, Connection Motif, and Three-Dimensional Architecture

Abstract

Seven perylene-porphyrin dyads were examined with the goal of identifying those most suitable for components of light-harvesting systems. The ideal dyad should exhibit strong absorption by the perylene in the green, undergo rapid and efficient excited-state energy transfer from perylene to porphyrin, and avoid electron-transfer quenching of the porphyrin excited state by the perylene in the medium of interest. Four dyads have different perylenes at the p-position of the meso-aryl group on the zinc porphyrin. The most suitable perylene identified in that set was then incorporated at the m- or o-position of the zinc porphyrin, affording two other dyads. An analogue of the o-substituted architecture was prepared in which the zinc porphyrin was replaced with the free base porphyrin. The perylene in each dyad is a monoimide derivative; the perylenes differ in attachment of the linker (either via a diphenylethyne linker at the N-imide or an ethynylphenyl linker at the C9 position) and the number (0-3) of 4-tert-butylphenoxy groups (which increase solubility and slightly alter the electrochemical potentials). In the p-linked dyad, the monophenoxy perylene with an N-imide diphenylethyne linker is superior in providing rapid and essentially quantitative energy transfer from excited perylene to zinc porphyrin with minimal electron-transfer quenching in both toluene and benzonitrile. The dyads with the same perylene at the m- or o-position exhibited similar results except for one case, the o-linked dyad bearing the zinc porphyrin in benzonitrile, where significant excited-state quenching is observed; this phenomenon is facilitated by close spatial approach of the perylene and porphyrin and the associated thermodynamic/kinetic enhancement of the electron-transfer process. Such quenching does not occur with the free base porphyrin because electron transfer is thermodynamically unfavorable even in the polar medium. The p-linked dyad containing a zinc porphyrin attached to a bis(4-tert-butylphenoxy)perylene via an ethynylphenyl linker at the C9 position exhibits ultrafast and quantitative energy transfer in toluene; the same dyad in benzonitrile exhibits ultrafast (<0.5 ps) perylene-to-porphyrin energy transfer, rapid (∼5 ps) porphyrin-to-perylene electron transfer, and fast (∼25 ps) charge recombination to the ground state. Collectively, this study has identified suitable perylene-porphyrin constructs for use in light-harvesting applications.