Laser flash photolysis study on the photoinduccd reactions of 3,3′-bridged bithiophenes

Mamoru Fujitsuka, Tadatake Sato, Fumiyasu Sezaki, Kazuyoshi Tanaka, Akira Watanabe, Osamu Ito

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31 Citations (Scopus)

Abstract

Photophysical properties and photoinduced reactions of 3,3′-bridged-2,2′-bithiophenes {dithieno[3,2-b:2′,3′-d]-thiophene, 4H-cyclopenta[2,1-b:3,4-b′]dithiophene, and 4H-dithieno[3,2-b;2′,3′-d]pyrrole (DTP)} and 2,2′-bithiophene (BT) were investigated by observing the transient absorption spectra in the visible and near-IR regions using nanosecond laser flash photolysis. Fluorescence quantum yields for the bridged bithiophenes were low compared with that for BT. An especially low quantum yield for DTP in acetonitrile was attributed to an addition reaction with the solvent. The triplet energy of BT was the lowest amongst the examined bithiophenes, indicating some conformational change in the triplet state. Triplet-energy-transfer reactions at diffusion limited rates were confirmed between bithiophenes and triplet-energy donors or acceptors. Photochemical generation of the radical cations of the bithiophenes was confirmed by the transient absorption spectra, which show good correspondence with those observed in γ-ray radiolysis. It was found that the triplet quenching rates of the electron-transfer reactions were small when the Gibbs energy change for the reaction was ≥ -25 kJ mol-1. The observed tendency agreed with the semi-empirical equation of Rehm-Weller. The generated radical cations decay according to a second-order function, indicating deactivation by a back electron-transfer reaction.

Original languageEnglish
Pages (from-to)3331-3337
Number of pages7
JournalJournal of the Chemical Society - Faraday Transactions
Volume94
Issue number22
DOIs
Publication statusPublished - 1998 Nov 21

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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