Keggin型硅钨酸盐[Cu(dap)_2(H_2O)][Cu(dap)_2][Na(H_2O)_5]H[SiW_(11)CuO_(39)]·H_2O的合成与结构(英文)  

Synthesis and structure of [Cu(dap)_2(H_2O)][Cu(dap)_2][Na(H_2O)_5]H[SiW_(11)CuO_(39)]·H_2O built by Keggin-type silicotungstate subunits

作　　者：陈利娟[1,2] 罗婕[1,2] 元静[1] 李慧颖[1] 

机构地区：[1]河南大学化学化工学院,河南开封475004 [2]河南大学基础实验教学中心,河南开封475004

出　　处：《化学研究》2012年第6期13-18,共6页Chemical Research

基　　金：Supported by the Natural Science Foundation of China(21101055);China Postdoctoral Science Foundation funded project(201104392,20100470996);the Natural Science Foundation of Henan Province(122300410106);the Foundation of Education Departmentof Henan Province(2009A150003,2010B150006)

摘　　要：在水热条件下,以Na10[A-α-SiW9O34].18H2O、氯化铜、四氮唑乙酸和1,2-丙二胺为原料合成了一种三维有机-无机杂化单铜取代Keggin型硅钨酸盐[Cu(dap)2(H2O)][Cu(dap)2][Na(H2O)5]H[α-SiW11CuO39].H2O(1),并借助元素分析、红外光谱和单晶X射线衍射对其进行了表征.结果表明,化合物1的分子结构片段由1个单铜取代Keggin型多金属氧酸盐单元[α-SiW11CuO39]6-,1个支撑的[Cu(dap)2(H2O)]2+配离子,1个[Cu(dap)2(H2O)]2+桥配离子,1个[Na(H2O)5]+离子和1个结晶水分子组成.在[α-SiW11CuO39]6-单元中,缺位位点完全被一个铜原子占据,而不是被半个铜原子和半个钨原子所占据.值得注意的是,每个分子结构片段与4个邻近相同片段相连构筑有机-无机杂化三维框架.A novel three dimensional（3-D） organic inorganic hybrid mono-copper substituted Keggin-type silicotungstate [ Cu（dap） 2（H 2 O）][ Cu（dap） 2 ][ Na（H 2 O） 5 ] H [ α-SiW 11 CuO 39 ].H 2 O（1）（dap=1,2-diaminopropane） was prepared by the hydrothermal reaction of Na10 [ A-α-SiW 9 O 34 ].18H 2 O,CuCl 2.2H 2 O,1H-tetrazole-1-acetic acid and dap.As-synthesized product was characterized by elemental analysis,infrared spectrometry and single-crystal X-ray diffraction.Results indicate that the molecular structural fragment of 1 contains a mono-copper substituted Keggin-type polyoxometalate subunit [ α-SiW 11 CuO 39 ] 6 –,one supporting [ Cu（dap） 2（H 2 O）] 2＋ cation,one bridging [ Cu（dap） 2 ] 2＋ cation,one [ Na（H 2 O） 5 ] ＋ cation,one proton and one lattice water molecule.The copper atom in the [ α-SiW 11 CuO 39 ] 6unit is perfectly located in the defect site other than simultaneously statistically occupied by copper Ⅱ and tungsten VI elements with half occupancy for each.Besides,it should be noted that each molecular structural fragment is combined with four identical neighboring ones constructing the organic inorganic hybrid 3-D framework.

关 键 词：多金属氧酸盐 硅钨酸盐 Keggin结构 三维框架 有机-无机杂化化合物 

分 类 号：O614.3[理学—无机化学]