Solvatochromic Shift of Aromatic Ketyl Anions due to Hydrogen Bonding.
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概要
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The electronic spectra of fluorenone radical anions generated by γ-irradiation at 77 K in glassy matrices of ethanol and ethanol–2-methyltetrahydrofuran mixtures have been measured for elucidating the mechanism of the spectral change due to solvation of the radical anions by alcohols. Three kinds of the radical anions are generated in the mixed solvent: the radical anions without hydrogen bond (ε=1.05×10<SUP>4</SUP> dm<SUP>3</SUP> mol<SUP>−1</SUP> cm<SUP>−1</SUP> at λ<SUB>max</SUB>=568 nm), with one ethanol molecule (ε=0.67×10<SUP>4</SUP> dm<SUP>3</SUP> mol<SUP>−1</SUP> cm<SUP>−1</SUP> at λ<SUB>max</SUB>=529 nm) and two ethanol molecules (ε=0.37×10<SUP>4</SUP> dm<SUP>3</SUP> mol<SUP>−1</SUP> cm<SUP>−1</SUP> at λ<SUB>max</SUB>=448 nm) hydrogen-bonded through the π electron on the carbonyl oxygen. The spectral shift and the decrease of the molar extinction coefficient of aromatic ketyl radical anions are explained as due to the stabilization of a carbonyl antibonding <I>n</I> orbital by hydrogen bonding.
- 公益社団法人 日本化学会の論文
著者
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Yoshida Hiroshi
Faculty Of Math Kyushu Univ.
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Ichikawa Tsuneki
Faculty of Engineering, Hokkaido University
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Ueda Ken-ichi
Faculty of Engineering, Hokkaido University
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Yoshida Hiroshi
Faculty of Engineering, Hokkaido University
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