Stilbene Dimer Radical Cations in the Radiolyses of Stilbenes and 1,2,3,4-Tetraphenylcyclobutanes

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  • Sachiko Tojo
    The Institute of Scientific and Industrial Research, Osaka UniversityMihogaoka 8-1, Ibaraki, Osaka 567
  • Kazuhiro Morishima
    The Institute of Scientific and Industrial Research, Osaka UniversityMihogaoka 8-1, Ibaraki, Osaka 567
  • Akito Ishida
    The Institute of Scientific and Industrial Research, Osaka UniversityMihogaoka 8-1, Ibaraki, Osaka 567
  • Tetsuro Majima
    The Institute of Scientific and Industrial Research, Osaka UniversityMihogaoka 8-1, Ibaraki, Osaka 567
  • Setsuo Takamuku
    The Institute of Scientific and Industrial Research, Osaka UniversityMihogaoka 8-1, Ibaraki, Osaka 567

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Abstract

<jats:title>Abstract</jats:title> <jats:p>The reaction of the stilbene radical cation formed by pulse radiolysis or γ-radiolyses is explained based on neutralization as well as the formation of a π-type stilbene dimer radical cation (π-St2+•), converting to the σ-type St2+• (σ-St2+•). The r-1,c-2,t-3,t-4-tetraphenylcyclobutane radical cation generated in a rigid matrix at 77 K which converted to σ-St2+• upon warming. Both r-1,c-2,t-3,t-4- and r-1,t-2,c-3,t-4-tetraphenylcyclobutane radical cations underwent photochemical cycloreversion to π-St2+• upon irradiation at wavelengths longer than 390 nm at 77 K, and converted to σ-St2+• upon warming. It is suggested that π-St2+• has overlapping arrangements of π-electrons, while σ-St2+• has radical and cation centers on the 1- and 4-positions of the C4 linkage.</jats:p>

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