以新型[Mo_8Na_2O_(28)]^(6-)多阴离子为建筑单元的2D→3D互锁配位聚合物的组装、结构及性质

A novel 2D→3D polycatenated coordination polymer based on a new [Mo_8Na_2O_(28)]^(6-) building unit: Assembly, structure and properties

以NiCl2、(NH4)6Mo7O24、NaOH及柔性配体1,3-二(1,2,4-三氮唑-1-)丙烷(Btp)为原料,采用水热技术合成了一个结构新颖的基于多金属氧酸盐(多酸)[Mo8Na2O28]6–的二维有机-无机杂化配位聚合物[Ni(Btp)2(H2O)Mo8Na2O26(μ2-OH)2]0.5·H2O(1).通过元素分析、IR、TG和X-射线单晶衍射等对化合物1进行了表征.X-射线单晶结构分析表明,该化合物属于单斜晶系,P21/c空间群,晶胞参数a=11.6871(8)?,b=21.7506(15)?,c=14.9208(8)?,Z=4,R1=0.0487,wR2=0.1409.化合物1中含有一种新型的多酸阴离子簇[Mo8Na2O28]6–,可以看作是由β-[Mo8O26]4–转化成的具有[V10O28]6–结构特征的新型多酸.该多酸被镍和Btp形成的二维(2D)层夹在中间,形成一种夹心型的2D柱状层结构.二维柱状层之间相互穿插形成了一个二维→三维(2D→3D)的互锁结构,柱状层之间的氢键作用又进一步稳固了整个框架.此外,该化合物具有较好的电催化和光催化性能.

A novel 2D inorganic-organic hybrid coordination polymer based on polyoxometalate [Mo8Na2O28]6–, [Ni（Btp）2（H2O）Mo8Na2O26（μ2-OH）2]0.5·H2O （1） （Btp = 1,3-bis（1,2,4-triazol-1-yl）propane）, has been prepared under hydrothermal reaction with a mixture of （NH4）6Mo7O24·4H2O, NiCl2·6H2O, flexible ligand （Btp）, NaOH and water, and structurally characterized by elemental analyses, IR spectroscopy, TG, and single-crystal X-ray diffraction analysis. X-ray crystal structure analysis shows that, the compound belongs to monoclinic crystal system, space group P21/c, crystal data： a = 11.6871（8） , b = 21.7506（15）, c = 14.9208（8） , Z = 4, R1 = 0.0487, wR2 = 0.1409. Compound 1 contains a kind of new polyoxometalate cluster [Mo8Na2O28]6–, which could be regarded as the transformation from β-[Mo8O26]4– and with the structural characteristics similar to [V10O28]6– polyanion. The polyoxometalates are sandwiched by the 2D layer constructed by NiII and Btp, leading to the formation of sandwich-like 2D columnar layer. The 2D columnar layer penetrates each other and finally results in the construction of an interesting 2D→3D polycatenated structure. In addition, the title complex shows good electrocatalytic and photocatalytic activity.