ESR and ENDOR studies of the ion pairs of double-, triple-, and quadruple-layered [2.2]paracyclophane radical anions and alkali metal cations.
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概要
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The radical anions of double-, triple-, and two kinds of quadruple-layered [2.2]paracyclophane XX<SUP>\newdot</SUP>, XDX<SUP>\newdot</SUP>, XDDX(C<SUB>2h</SUB>)<SUP>\newdot</SUP> and XDDX(D<SUB>2</SUB>)<SUP>\newdot</SUP> were examined by means of ESR and ENDOR spectroscopy. The spin distributions in these radical anions are largely polarized by interaction with counter ions. An MO calculation has been attempted to account for the observed ion-pairing effects. It is shown by the calculations that the observed ion-pairing effects can be explained by the ion-pair models where the cation is located above the center of the outermost benzene ring. It is also shown that the potassium ion migrates from one side of the radical molecule to the other in a loosely bound ion pair of XDX<SUP>\newdot</SUP> in a 1,2-dimethoxyethane(DME)-tetrahydrofuran(THF) 1:1 mixed solvent, as in the ion pair of XX<SUP>\newdot</SUP> with the potassium ion in DME-THF (2:1) which has been previously reported by Gerson <I>et al.</I> Such migration of cations in ion pairs was not observed for the quadruple-layered [2.2]paracyclo-phane radical anions.
- 公益社団法人 日本化学会の論文
著者
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Yamamoto Takamitsu
Analytical Instrument Division Jeol Ltd.
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Iwaizumi Masamoto
Chemical Research Institute of Non-Aqueous Solutions, Tohoku University
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Isobe Taro
Chemical Research Institute of Non-Aqueous Solutions, Tohoku University
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Kita Shouichi
Chemical Research Institute of Non-Aqueous Solutions, Tohoku University
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Horita Hisanori
The Institute of Scientific and Industrial Research, Osaka University
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Yamamoto Takamitsu
Analytical Instrument Division, JEOL, Ltd.
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Kohno Masahiro
Analytical Instrument Division JEOL
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Otsubo Tetsuo
Analytical Instrument Division, JEOL, Ltd.
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Misumi Soichi
Chemical Research Institute of Non-Aqueous Solutions, Tohoku University
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