- 著者
-
Sasaki Yoh
Yamase Toshihiro
Ohashi Yuji
Sasada Yoshio
- 出版者
- The Chemical Society of Japan
- 雑誌
- Bulletin of the Chemical Society of Japan (ISSN:00092673)
- 巻号頁・発行日
- vol.60, no.12, pp.4285-4290, 1987
- 被引用文献数
-
34
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.