化学学报 ›› 2007, Vol. 65 ›› Issue (17): 1826-1830. 上一篇    下一篇

研究论文

含新颖一维金属氧簇阳离子的聚金属氧簇化合物[{M(2,2'-bipy)}5O14]4- [2,2'-H2bipy]2(As2W18O62)2•8H2O (M=Mo, W)的合成、晶体结构与表征

王敬平, 王伟, 刘迎红, 牛景杨*   

  1. (河南大学化学化工学院 分子与晶体工程研究所 开封 475001)
  • 投稿日期:2006-12-26 修回日期:2007-03-13 发布日期:2007-09-14
  • 通讯作者: 牛景杨

Synthesis, Crystal Structure and Characterization of a Polyoxometa-late Containing a Novel 1D Polycation Chain: [{M(2,2'-bipy)}5O14]4- [2,2'-H2bipy]2(As2W18O62

WANG Jing-Ping; WANG Wei; LIU Ying-Hong; NIU Jing-Yang*   

  1. (Institute of Molecular and Crystal Engineering, School of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001)
  • Received:2006-12-26 Revised:2007-03-13 Published:2007-09-14
  • Contact: NIU Jing-Yang

以Na2WO4•2H2O, Na2MoO4•2H2O, Na2HAsO4•7H2O和2,2'-bipyridine为原料, 在水热条件下制得了含一维阳离子的聚金属氧簇化合物: [{M(2,2'-bipy)}5O14]4[2,2'-H2bipy]2(As2W18O62)2•8H2O (M=Mo/W; 2,2'-bipy=2,2'-bipyridyl), 并用元素分析, IR, TG和单晶X-ray衍射等手段进行了表征. 标题化合物属于单斜晶系, C2/c空间群, a=4.1721(5) nm, b=2.4629(5) nm, c=1.7541(5) nm, β=91.119(3)°, V=18.021(5) nm3, Z=2, R1=0.0629, wR2=0.1605 [I>2σ(I)]. 标题化合物的阳离子链由五元金属氧簇构筑块[{M(2,2'-bipy)}5O14]2+通过氧原子桥联而成, 构筑块[{M(2,2'-bipy)}5O14]2+中的五个金属原子呈畸变的“A”字型排布, 阳离子展现出新颖的一维锯齿链状结构.

关键词: 聚金属氧簇化合物, 晶体结构, 水热合成, Dawson结构

A novel polyoxometalate containing a 1-D cation chain [{M(2,2'-bipy)}5O14]4[2,2'-H2bipy]2(As2W18O62)2•8H2O (M=Mo/W; 2,2'-bipy=2,2'-bipyridyl) has been synthesized by the hydrothermal reaction of Na2WO4•2H2O, Na2MoO4•2H2O, Na2HAsO4•7H2O and 2,2'-bipyridyl, and characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction. The title compound is monoclinic with a C2/c space group, a=4.1721(5) nm, b=2.4629(5) nm, c=1.7541(5) nm, β=91.119(3)°, V=18.021(5) nm3, Z=2, R1=0.0629, wR2=0.1605 [I>2σ(I)]. The cation chain in the title compound is built up from the quintuple polyoxometalate unit [{M(2,2'-bipy)}5O14]2+, in which five metal atoms exhibit the distorted “A” configuration, and each [{M(2,2'-bipy)}5O14]2+ unit is connected to adjacent blocks by bridging-oxygen atoms. The 1-D cation chain shows the zigzag structure.

Key words: polyoxometalate, crystal structure, hydrothermal synthesis, Dawson structure