Synthesis and photoinduced electron transfer processes of rotaxanes bearing [60]fullerene and zinc porphyrin: Effects of interlocked structure and length of axle with porphyrins

Atula S.D. Sandanayaka, Nobuhiro Watanabe, Kei Ichiro Ikeshita, Yasuyuki Araki, Nobuhiro Kihara, Yoshio Furusho, Osamu Ito, Toshikazu Takata

Research output: Contribution to journalArticle

64 Citations (Scopus)

Abstract

Three rotaxanes, with axles with two zinc porphyrins (ZnPs) at both ends penetrating into a necklace pending a C60 moiety, were synthesized with varying interlocked structures and axle lengths. The intra-rotaxane photoinduced electron transfer processes between the spatially positioned C 60 and ZnP in rotaxanes were investigated. Charge-separated (CS) states (ZnṖ+, C60̇-) rotaxane are formed via the excited singlet state of ZnP ( 1ZnP*) to the C60 moiety in solvents such as benzonitrile, THF, and toluene. The rate constants and quantum yields of charge separation via 1ZnP* decrease with axle length, but they are insensitive to solvent polarity. When the axle becomes long, charge separation takes place via the excited triplet state of ZnP (3ZnP*). The lifetime of the CS state increases with axle length from 180 to 650 ns at room temperature. The small activation energies of charge recombination were evaluated by temperature dependence of electron-transfer rate constants, probably reflecting through-space electron transfer in the rotaxane structures.

Original languageEnglish
Pages (from-to)2516-2525
Number of pages10
JournalJournal of Physical Chemistry B
Volume109
Issue number7
DOIs
Publication statusPublished - 2005 Feb 24

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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