Triplet Intermediates in Cis-Trans Photoisomerization of 3-Chrysenylethylenes.

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概要

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• The effect of substitution of 3-chrysenyl group (Ar) on unsaturated double bonds in their triplet sensitized isomerization was investigated for Ar–CH=CH–R, R=′Bu (BC) and Ph (SC) by means of stationary irradiations, laser flash photolyses, and MO calculations. Both olefins undergo mutual isomerization between their cis- and trans-isomers. However, BC has a unique triplet energy surface with two decay funnels at the planar trans (<SUP>3</SUP>t<SUP>*</SUP>) and twisted (<SUP>3</SUP>p<SUP>*</SUP>) conformations, which are in equilibrium with each other; <SUP>3</SUP>t<SUP>*</SUP> undergoes either unimolecular decay to the ground-state trans isomer or triplet energy transfer to the cis isomer (quantum chain process) and <SUP>3</SUP>p<SUP>*</SUP> decays to the ground state to give the cis and trans isomers. T<I><SUB>n</SUB></I>←T<SUB>1</SUB> absorptions observed for BC and SC are mainly attributed to <SUP>3</SUP>t<SUP>*</SUP> and <SUP>3</SUP>p<SUP>*</SUP>, respectively, on the basis of semiempirical MO calculations. The populations at <SUP>3</SUP>t<SUP>*</SUP> and <SUP>3</SUP>p<SUP>*</SUP> are estimated.

• 公益社団法人 日本化学会の論文

著者

• Arai Tatsuo

  Department Of Applied Physics Nagoya University

• Karatsu Takashi

  College Of Arts And Sciences Chiba University

• Sakuragi Hirochika

  Department Of Chemistry University Of Tsukuba

• Tokumaru Katsumi

  Department of Chemistry Faculty of Science The University of Tokyo

• Tokumaru Katsumi

  Department of Chemistry, The University of Tsukuba

• Hiresaki Tatsuro

  Department of Chemistry, The University of Tsukuba

• Wirz Jakob

  Institut für Physikalische-Chemie der Universität Basel

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