Mechanistic approach to the sensitization process of aromatic ketones in the isomerization between norbornadiene and quadricyclane.
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概要
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The quantum yields for norbornadiene(N)→quadricyclane(Q) and Q→N isomerization were determined in acetonitrile using several substituted benzophenones (BPs) as triplet sensitizers. For the N→Q isomerization, BPs with electron-donating substituents exhibited higher quantum efficiency (0.4–0.6) than BPs with electronaccepting substituents. The quantum yields for Q→N isomerization increased with electron-accepting ability of the substituents on BPs, but were lower than 0.1. The rate constants for quenching of triplet BPs by N and Q were also determined in acetonitrile by means of laser flash photolysis. The rate constants for N were not dependent on the triplet energies (<I>E</I><SUB>T</SUB>) of BPs but dependent on electronic properties of the substituents on BPs. On the contrary, those for Q increased with decreasing <I>E</I><SUB>T</SUB> of BPs and with increasing Hammett's σ constants of the substituents of BPs. Based on these observations an addition-elimination process is proposed for the N→Q isomerization, and an electron transfer process for the Q→N isomerization.
- 公益社団法人 日本化学会の論文
著者
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OGUCHI Takahisa
Department of Chemistry, University of Tsukuba
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Arai Tatsuo
Department Of Applied Physics Nagoya University
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Sakuragi Hirochika
Department Of Chemistry University Of Tsukuba
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WAKABAYASHI Toshio
Department of Communication Engineering
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Nishimura Yoshinobu
Department Of Chemical Process Engineering Faculty Of Engineering Hokkaido University
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Tokumaru Katsumi
Department of Chemistry Faculty of Science The University of Tokyo
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TSUCHIYA Masahiro
Department of Chemistry, University of Tsukuba
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Tsuchiya Masahiro
Department of Aging and Geriatric Dentistry, Graduate School of Dentistry, Tohoku University
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Oishi Shigero
Sagami Chemical Research Center
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Wakabayashi Toshio
Department of Chemistry, University of Tsukuba
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