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

Yusuke Kuramochi, Atula S.D. Sandanayaka, Akiharu Satake, Yasuyuki Araki, Kazuya Ogawa, Osamu Ito, Yoshiaki Kobuke

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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 fullero-pyrrolidine moieties (C60-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 1.4 × 107 and 1.6 × 10 7M-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 C60-ZnP-Tripod, the converged energy at the ZnP moiety induced electron transfer to the C60 moiety, which afforded the stable charge-separated state (φCS > 90%).

Original languageEnglish
Pages (from-to)2317-2327
Number of pages11
JournalChemistry - A European Journal
Volume15
Issue number10
DOIs
Publication statusPublished - 23 Feb 2009

Keywords

  • Fullerenes
  • Photochemistry
  • Photosynthesis
  • Porphyrinoids
  • Self-assembly

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