Decay mechanism of the aromatic hydrocarbon biradical, 1,1'-biacenaphthene-2,2'-diyl. Effects of solvent and heavy-atom perturbation.
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概要
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Effects of solvents and heavy-atom (H–A) containing compounds on the lifetime of the title biradical (<B>1</B>) have been examined to elucidate the decay mechanism of <B>1</B> in fluid solutions by means of nanosecond laser spectroscopy. <B>1</B> was quenched effectively by H–A compounds such as diethylmercury and iodoethane. The decay rates of <B>1</B> showed no explicit correlation with solvent polarities, while a linear correlation was found between the decay rate and the sum of squares of the spin-orbit (S–O) coupling factors of heavy atoms involved in the solvents; chlorobezene, 1,2-dichloroethane, dichloromethane, bromobenzene, and dibromomethane. It has been shown that (i) the biradical lifetime is determined by intersystem crossing (ISC) from the triplet to singlet spin state prior to chemical reactions, (ii) ISC is enhanced by H–A perturbation through the S–O interaction, and (iii) the reactivity of the singlet biradical (<SUP>1</SUP><B>1</B>) but not the triplet one (<SUP>3</SUP><B>1</B>) sways the product distribution in the triplet-sensitized photodimerization of acenaphthylene.
- 公益社団法人 日本化学会の論文
著者
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Morita Toshifumi
Department Of Aerospace Engineering College Of Science And Technology Nihon University
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Kobashi Harumichi
Department of Chemistry, Faculty of Engineering, Gunma University
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Kobashi Harumichi
Department of Chemistry, Faculty of Engineering Gunma University
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Ikawa Hiroki
Department of Chemistry, Faculty of Engineering, Gunma University
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Kondo Reiko
Department of Chemistry, Faculty of Engineering, Gunma University
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