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.
出处
《化学研究》
CAS
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)
