V-Shaped Polyoxotungstoarsenates Incorporating a Prism-Like Hexa Transition-Metals Center : [M_6(H_2O)_2(AsW_9O_<34>)_2(AsW_6O_<26>)]^<17-> (M^<2+> = Mn^<2+>, Co^<2+>, Zn^<2+>)

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Hexa transition-metals incorporated polyoxotungstoarsenates, [M<SUB>6</SUB>(H<SUB>2</SUB>O)<SUB>2</SUB>(AsW<SUB>9</SUB>O<SUB>34</SUB>)<SUB>2</SUB>(AsW<SUB>6</SUB>O<SUB>26</SUB>)]<SUP>17−</SUP> (M<SUP>2+</SUP> = Mn<SUP>2+</SUP>, Co<SUP>2+I</SUP>, Zn<SUP>2+</SUP>), have been prepared at pH 7–8 and characterized by elemental analysis, electrochemistry, and X-ray crystallography: Na<SUB>17</SUB>[Mn<SUB>6</SUB>(H<SUB>2</SUB>O)<SUB>2</SUB>(AsW<SUB>9</SUB>O<SUB>34</SUB>)<SUB>2</SUB>(AsW<SUB>6</SUB>O<SUB>26</SUB>)]·41H<SUB>2</SUB>O (<B>1</B>), <I>P</I>2<SUB>1</SUB>/<I>c</I>, <I>a</I> = 17.73(1) Å, <I>b</I> = 22.34(1) Å, <I>c</I> = 35.41(3) Å, β = 95.37(3)°, <I>V</I> = 13963(14) Å<SUP>3</SUP>, and <I>Z</I> = 4; Na<SUB>17</SUB>[Co<SUB>6</SUB>(H<SUB>2</SUB>O)<SUB>2</SUB>(AsW<SUB>9</SUB>O<SUB>34</SUB>)<SUB>2</SUB>(AsW<SUB>6</SUB>O<SUB>26</SUB>)]·41H<SUB>2</SUB>O (<B>2</B>), <I>P</I>2<SUB>1</SUB>/<I>c</I>, <I>a</I> = 17.65(1) Å, <I>b</I> = 22.24(1) Å, <I>c</I> = 34.78(2) Å, β = 95.84(2)°, <I>V</I> = 13584(13) Å<SUP>3</SUP>, and <I>Z</I> = 4; Na<SUB>17</SUB>[Zn<SUB>6</SUB>(H<SUB>2</SUB>O)<SUB>2</SUB>(AsW<SUB>9</SUB>O<SUB>34</SUB>)<SUB>2</SUB>(AsW<SUB>6</SUB>O<SUB>26</SUB>)]·38H<SUB>2</SUB>O (<B>3</B>), <I>P</I>2<SUB>1</SUB>/<I>c</I>, <I>a</I> = 17.6295(6) Å, <I>b</I> = 22.2992(7) Å, <I>c</I> = 34.927(1) Å, β = 95.695(2)°, <I>V</I> = 13662.8(7) Å<SUP>3</SUP>, and <I>Z</I> = 4. The anion of <B>1</B>–<B>3</B> consists of two B-α [{M(H<SUB>2</SUB>O)}M<SUB>2</SUB>(AsW<SUB>9</SUB>O<SUB>34</SUB>)]<SUP>3−</SUP> units joined by a B-type hexa-vacant [AsW<SUB>6</SUB>O<SUB>26</SUB>]<SUP>11−</SUP> fragment, corresponding to a removal of the edge-sharing W<SUB>3</SUB>O<SUB>8</SUB> moiety from B-α [AsW<SUB>9</SUB>O<SUB>34</SUB>]<SUP>9−</SUP>, to form a <I>C</I><SUB>2<I>v</I></SUB>-symmetric V-shaped geometry. Two edge-sharing MO<SUB>6</SUB>-octahedral triads (with M···M distances 3.2–3.4 Å) are well-separated with M···M distances of 5.5–8.9 Å. Three successive electrochemically quasi-reversible two-electron Mn<SUP>II</SUP>/Mn<SUP>III</SUP> waves were observed in the cyclic voltammogram of <B>1</B>. M<SUP>2+</SUP> ion with larger radius causes an elongation of the As···As distances. A single Na<SUP>+</SUP> cation coordinated by three oxygen atoms (two belonging to B-α [AsW<SUB>9</SUB>O<SUB>34</SUB>]<SUP>9−</SUP> and one belonging to B-[AsW<SUB>6</SUB>O<SUB>26</SUB>]<SUP>11−</SUP>) in the crevice of the anion stabilizes the V-shaped structure.

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  • Bulletin of the Chemical Society of Japan  

    Bulletin of the Chemical Society of Japan 80(1), 178-182, 2007-01-15 

    The Chemical Society of Japan

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各種コード

  • NII論文ID(NAID)
    10018708646
  • NII書誌ID(NCID)
    AA00580132
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    00092673
  • NDL 記事登録ID
    8603578
  • NDL 雑誌分類
    ZP1(科学技術--化学・化学工業)
  • NDL 請求記号
    Z53-B35
  • データ提供元
    CJP書誌  NDL  J-STAGE 
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