利用水热合成技术制备了基于半刚性双吡啶双酰胺配体L(N,N′-双(4-吡啶甲酰胺)-1,2-环己烷)和Keggin型多金属氧酸盐的铜功能配合物[Cu2(L)2(Si W(12)O(40))(H2O)8]·H2O,并通过元素分析、红外光谱和X-射线单晶衍射方法确定了该配合物的晶体结构.结构分析表明该化合物属于三斜晶系,P1-空间群,晶胞参数a=1.153 10(10)nm,b=1.339 10(12)nm,c=1.429 40(12)nm,α=71.514 0(10)°,β=66.926 0(10)°,γ=68.111 0(10)°,V=1.846 0(3)nm-3,Z=1,R1=0.067 3,w R2=0.181 1.配合物由离散的[Si W(12)O(40)]-(4-)杂多阴离子和[Cu2(L)2(H2O)8]-(4+)阳离子组成,2种结构单元间通过氢键作用形成二维超分子层结构.标题配合物修饰的碳糊电极对NO-(2-)还原有较好的电催化活性,而且该配合物对降解亚甲蓝分子有显著的光催化效率.
A new copper compound based on Keggin-type polyoxometalate and a semi-rigid bis-pyridylbis-amide ligand L(N,N′-bis(4-pyridinecarboxamide)-1,2-cyclohexane), [Cu2(L)2(Si W(12)O(40))(H2O)8]·H2O, has been hydrothermally synthesized and characterized by elemental analysis, IR and single crystal X-ray diffraction. The title ompound crystallizes in the triclinic system, space group P1, a=1.153 10(10) nm, b=1.339 10(12) nm, c=1.429 40(12) nm, α=71.514 0(10)°, β=66.926 0(10)°, γ=68.111 0(10)°, V=1.846 0(3) nm-3, Z=1, R1=0.067 3, w R2=0.181 1. It consists of the discrete [Si W(12)O(40)]-(4-) polyoxometalate anion and [Cu2(L)2(H2O)8]-(4+) cation, then both units are connected by the hydrogen bonding interactions to give a two-dimensional supramolecular layer. The title compound modified carbon paste electrode displays a good electrocatalytic activity towards reduction of NO-(2-). Moreover, the compound possesses an excellent photocatalytic efficiency for the degradation of methylene blue molecule.