基于多金属氧酸盐构筑的三维倾斜连锁网络

Three-dimensional inclined catenation network based on polyoxometalate

多酸化学是当前无机化学和配位化学研究的热点研究领域之一,多酸化合物在材料、医药和催化领域具有重要的潜在应用。通过利用Keggin型多酸阴离子[H3PMo12O40],4,4’-联吡啶和Cu离子在水热条件下合成了2例多酸基无机-有机杂化化合物,(H24,4’-bpy)2(PMo12O40)·(4,4’-bpy)·4(H2O)(1)和[Cu4(4,4’-bpy)7(PMo12O40)]·4(H2O)(2)。化合物1结晶于单斜晶系,空间群C2/c,晶胞参数a=1.5241(3)nm,b=1.8152(4)nm,c=2.1210(4)nm,β=103.35(3)°,V=5.170(2)nm3,化合物2结晶于正交晶系,空间群Pbam,晶胞参数a=2.2586(5)nm,b=1.2962(3)nm,c=1.5573(3)nm,V=4.559(2)nm3。化合物1是由Keggin型多阴离子和4,4’-联吡啶构筑的三维超分子网络;化合物2是由Keggin型多阴离子,4,4’-联吡啶和Cu离子构筑的具有(6,3)拓扑二维层状化合物,有趣的是,二维层相互缠结形成三维倾斜连锁网络。研究表明,过渡金属离子的加入对于调控整个体系的结构、维数等都起到十分重要的影响。

The chemistry of polyoxometalate is one of the exciting researh field of inorganic chemistry and coordination chemistry. Polyoxometalate have important applications in the material,biochemistry and catalysis chemistsry. Two new polyoxometalate-based compounds,（H24,4＇-bpy）2（PMo12O40）·（4,4＇-bpy）·4（H2O） （1） and [Cu4（4,4＇-bpy）7（PMo12O40）]·4（H2O） （2）,have been synthesized under hydrothermal conditions by using [H3PMo12O40],4,4＇-bpy and Cu ion. Compound 1 crystalized in the monoclinic,space guoup C2/c,a=1.524 1（3） nm,b=1.815 2（4） nm,c=2.121 0（4） nm,β=103.35（3）°,V= 5.170（2） nm3,compound 2 crystalized in the orthorhombic,space guoup Pbam,a=2.258 6（5） nm,b=1.296 2（3） nm,c=1.557 3（3） nm,V=4.559（2） nm3. Compound 1 exhibits a three-dimensional supramolecular network,formed by Keggin-type polyoxoanions and 4,4＇-bpy. Compound 2 exhibits a two-dimensional （6,3）-layered structure formed by Keggin-type polyoxoanions,4,4＇-bpy and Cu ions,and interestingly,these layers are entangled with each other to give a three-dimensional inclined catenated framework. These results show that the structure and dimension of the crystal can be regulated when the matal ion was introduced into the reaction system.