ESR and ENDOR studies of azulenophane anion radicals.
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概要
- 論文の詳細を見る
The anion radicals of <I>syn</I>- and <I>anti</I>-[2.2](2,6)azulenophane, (<B>1</B>) and (<B>2</B>), [2.2](1,3)azulenophane, (<B>3</B>), and [2](1,3)-azuleno[2]paracyclophane, (<B>4</B>), all produced by alkali metal reduction in various solvents, have been investigated by ESR and ENDOR spectroscopy. They exist in the ion pair with cations in the solutions, except for <B>4</B><SUP>\newdot</SUP> which exists in 1,2-dimethoxyethane with Na<SUP>+</SUP>. Their ion pairing tendency is appreciably higher than that of the naphthalenophane anion radicals. The unpaired electron in these ion pairs localizes mostly on an azulene ring (in <B>1</B><SUP>\newdot</SUP>, <B>2</B><SUP>\newdot</SUP>, and <B>3</B><SUP>\newdot</SUP>, close to a cation). The polarization effects due to the pairing with the cations are much larger than those in the naphthalenophane anion radicals, and increase in the order <B>1</B><SUP>\newdot</SUP>≤<B>2</B><SUP>\newdot</SUP>≤<B>3</B><SUP>\newdot</SUP>, indicating that the smaller the inter-layer orbital overlap, the larger the polarizability. The unpaired electron of <B>4</B><SUP>\newdot</SUP> localizes mostly on the azulene ring even in the free anion.
- 公益社団法人 日本化学会の論文
著者
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Kato Nobuo
Department Of Agricultural Chemistry Faculty Of Agriculture Kyoto University
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Fukazawa Yoshimasa
Department Of Chemistry Faculty Of Science Hiroshima University
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Ito Sho
Department Of Chemistry Faculty Of Science Tohoku University
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Iwaizumi Masamoto
Chemical Research Institute of Non-Aqueous Solutions, Tohoku University
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