钼钒氧簇二聚体[Ni(enMe)_2]_4{[Ni(enMe)_2][Ni(enMe)_2(H_2O)]_2[Mo_8~(Ⅵ)V_6~(Ⅳ)O_(38)(V~ⅤO_4)]_2}·8H_2O的合成与结构表征(英文)

在水热条件下合成了一例新型的多金属氧酸盐二聚物,Ni(enMe)2]4{Ni(enMe)2]Ni(enMe)2(H2O)]2Mo8ⅥV6ⅣO38(VⅤO4)]2}.8H2O(1)(enMe=1,2-丙二胺),利用元素分析、红外光谱分析、粉末X射线衍射、热重分析和单晶X射线衍射表征了其结构。结果表明,化合物(1)属于单斜晶系,P2(1)/n空间群.晶胞参数为a=1.9685(4)nm,b=1.3549(3)nm,c=2.7039(5)nm,α=90°,β=93.94(3)°,γ=90°,V=7.195(2)nm3,Z=4,Dc=2.390g/cm3,Mr=2588.4,μ=3.195mm-1,F(000)=5012,最终R1=0.0743,wR2=0.1861.与此同时,(1)是第一个具有二帽-Keggin型钼钒氧簇的二聚体,它由过渡金属部分Ni(enMe)2(H2O)]22+连接形成{Ni(enMe)2]Ni(enMe)2(H2O)]2Mo8ⅥV6ⅣO38(VⅤO4)]2}8-二聚阴离子.

Synthesis and Structural Characterization of Dimeric Molybdenum-Vanadium Clusters [Ni(enMe)2]4{[Ni(enMe)2] [Ni(enMe)2(H2O)]2[MoⅥ8VⅣ6O38(VⅤO4)]2}·8H2O

A novel polyoxometalate dimmer, Ni(enMe)2]4{Ni(enMe)2]Ni(enMe)2(H2O)]2MoⅥ8VⅣ6O38(VⅤO4)]2}·8H2O (1)(enMe = 1,2-diaminopropane), was synthesized under hydrothermal conditions. The structure of synthesized product (1) was characterized by means of elemental analysis, infrared spectrometry, powder X-ray diffraction, thermogravimetry, and single-crystal X-ray diffraction. Results indicate that product (1) crystallizes in monoclinic system and belongs to space group P2(1)/n with a = 1.968 5(4) nm, b = 1.354 9(3) nm, c = 2.703 9(5) nm, α = 90 °, β = 93.94(3) °, γ = 90 °, V = 7.195(2) nm3, Z = 4, Dc = 2.390 g/cm3, Mr = 2 588.4, μ = 3.195 mm-1, F(000) = 5 012, final R1 = 0.074 3, and wR2 = 0.186 1. At the same time, (1) is the first isolated dimmer with bi-capped Keggin molybdenum-vanadium clusters containing dimeric polyanion {Ni(enMe)2]Ni(enMe)2(H2O)]2MoⅥ8VⅣ6O38(VⅤO4)]2}8- which is linked by way of transition metal coordination fragment Ni(enMe)2(H2O)]2+2.