Hydrate Crystals of Alkali Metal-Chloranil and -Bromanil Salts and Their Optical and Magnetic Properties
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概要
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The potassium-chloranil (K<SUP>+</SUP>·CA<SUP>−</SUP>), sodium-chloranil (Na<SUP>+</SUP>·CA<SUP>−</SUP>) and sodium-bromanil (Na<SUP>+</SUP>·BA<SUP>−</SUP>) salts were found to form hydrates when their crystalline powders are exposed to a humid air. In the single crystal spectrum of K<SUP>+</SUP>·CA<SUP>−</SUP>, the charge-transfer band significantly increased its intensity on hydration, exhibiting the same polarization as in the spectrum of the water-free state. It was concluded that CA<SUP>−</SUP> ions in the hydrate crystal are closely stacked on each other to form columns as in the water-free crystal and the charge transfer interaction between CA<SUP>−</SUP> ions is stronger in the hydrate crystal than in the water-free crystal. The spin concentration of K<SUP>+</SUP>·CA<SUP>−</SUP> markedly decreased on hydration, it being 2.2×10<SUP>22</SUP> spins per mol in the state of hydrate while 5.5×10<SUP>23</SUP> spins per mol in the water-free state. The hydration resulted in an increase of the intensity of charge-transfer band and a decrease of the spin concentration also in the cases of Na<SUP>+</SUP>·CA<SUP>−</SUP> and Na<SUP>+</SUP>·BA<SUP>−</SUP>. It is also shown that organic solvents such as acetone, methy ethyl ketone and dichloromethane can enter into the crystal lattice of K<SUP>+</SUP>·CA<SUP>−</SUP> to form the solvent-containing crystals.
- 公益社団法人 日本化学会の論文
著者
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Kuroda Haruo
Department of Chemistry and Research Center for Spectrochemistry, Faculty of Science, The University of Tokyo
-
Hiroma Shoji
Department of Chemistry, Faculty of Science, The University of Tokyo
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