Energy Transfer Followed by Electron Transfer in a Porphyrin Macrocycle and Central Acceptor Ligand: A Model for a Photosynthetic Composite of the Light‐Harvesting Complex and Reaction Center

Abstract

A system that models a photosynthetic composite of the light-harvesting complex and reaction center is reported in which light energy collected by cyclic antenna porphyrins is transferred to a central energy-acceptor porphyrin, followed by photoinduced electron transfer to a fullerene positioned above the ring plane. Pyridyl tripodal ligands appended with bis(phenylethynyl)porphyrinatozinc(II) (ZnP-Tripod) and additional fulleropyrrolidine moieties (C(60)-ZnP-Tripod) were synthesized as the reaction center units. The tripodal ligand was strongly accommodated by the light-harvesting porphyrin macrocycle N-(1-Zn)(3) (1-Zn = trisporphyrinatozinc(II)) by using three-point coordination of pyridyl to uncoordinated porphyrinatozinc sites to afford a stable 1:1 composite. The binding constants for ZnP-Tripod and C(60)-ZnP-Tripod in benzonitrile were estimated from steady-state fluorescence titrations to be 1.4x10(7) and 1.6x10(7) M(-1), respectively. The steady-state fluorescence titration, fluorescence lifetime, and transient absorption studies revealed that in both composites the excitation energy collected by the nine porphyrins of N-(1-Zn)(3) was efficiently transferred to a ZnP moiety by means of a through-space mechanism with a quantum yield of approximately 90%. Furthermore, in the composite with C(60)-ZnP-Tripod, the converged energy at the ZnP moiety induced electron transfer to the C(60) moiety, which afforded the stable charge-separated state (Phi(CS)>90%).