Structural retention of decatungstates upon photoreduction.
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概要
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The crystal structures of oxidized and photoreduced decatungstates are compared. Three specimens of decatungstate complexes were prepared in mixed solvents of H<SUB>2</SUB>O–CH<SUB>3</SUB>CN and were characterized by X-ray diffraction. Unit cell parameters are as follows: (C<SUB>6</SUB>H<SUB>16</SUB>N)<SUB>4</SUB>[W<SUB>10</SUB>O<SUB>32</SUB>]·2CH<SUB>3</SUB>CN; DECA <I>M<SUB>r</SUB></I>=2841.4, monoclinic, <I>P</I>2<SUB>1</SUB>⁄<I>n</I>, <I>a</I>=14.617(2), <I>b</I>=17.783(3), <I>c</I>=11.755(2) Å, β=100.27(2)°, <I>V</I>=3006.5(9) Å<SUP>3</SUP>, <I>Z</I>=2; (C<SUB>6</SUB>H<SUB>16</SUB>N)<SUB>4</SUB>[H<SUB>1.5</SUB>W<SUB>10</SUB>O<SUB>32</SUB>]·8H<SUB>2</SUB>O; RED1 <I>M<SUB>r</SUB></I>=2905.4, monoclinic, <I>P</I>2<SUB>1</SUB>⁄<I>n</I>, <I>a</I>=15.902(3), <I>b</I>=12.233(2), <I>c</I>=15.673(4) Å, β=93.76(2)°, <I>V</I>=3042(1), Å<SUP>3</SUP> <I>Z</I>=2; Na<SUB>4</SUB>[H<SUB>1.8</SUB>W<SUB>10</SUB>O<SUB>32</SUB>]·14H<SUB>2</SUB>O; RED2 <I>M<SUB>r</SUB></I>=2696.7, monoclinic, <I>C</I>2⁄<I>m</I>, <I>a</I>=16.123(5), <I>b</I>=12.636(3), <I>c</I>=12.168(4) Å, β=117.40(2)°, <I>V</I>=2202(1) Å<SUP>3</SUP>, <I>Z</I>=2; There is no obvious change in the anion frame among the three decatungstate complexes. Photoreduced decatungstates may coordinate protons which neutralize excess charge injected into anions. It is concluded that the structure of W<SUB>10</SUB>O<SUB>32</SUB> is not largely altered up to two-electron reduction.
- 公益社団法人 日本化学会の論文
著者
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OHASHI Yuji
Department of Chemistry and Materials Science Tokyo Institute of Technology
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Yamase Toshihiro
Research Laboratory Of Resources Utilization Tokyo Institute Of Technology
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Sasada Yoshio
Department of Life Science, Tokyo Institute of Technology
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Sasaki Yoh
Research Laboratory of Resources Utilization, Tokyo Institute of Technology
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Ohashi Yuji
Department of Life Science, Tokyo Institute of Technology
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