采用水热合成法合成了一种结构新颖的多硼钒氧簇化合物(H2dap)6H［V12B16O54(OH)4］·12H2O(dap=1,2-diaminopropane), 对化合物1进行了单晶X射线衍射, 结果表明化合物1属于单斜晶系, C2/c空间群, 晶胞参数a=19.027(4), b=16.142(3), c=26.679(5), α=90°, β=101.06(3)°, γ=90°, V=8 042(3) nm3, Z=4, Dc=1.962 g·cm－3, μ=1. 456 mm－1, F(000)=4 776, 7 635个可观察独立衍射点射点［I>2σ(I)］, 最后结构精修到偏离因子R1=0. 0626, wR2=0.192 7, S=1.003。 该化合物的结构主要由V12B16簇单元和作为抗衡离子的1,2-丙二胺组成, 且簇单元之间通过强氢键N—H…O和弱氢键C—H…O的作用连接成了二维的层状结构, 层与层之间也是通过氢键的作用连接成了三维的超分子结构。 此外, 对化合物1进行了红外光谱、 磁微扰下的二维红外相关光谱、 热微扰下的二维红外相关光谱以及紫外-可见固体漫反射光谱分析的表征, 探讨了化合物1的结构与谱学性质的关系。 红外光谱表明νas(V—Oμ)反对称伸缩振动吸收峰和νs(V—Oμ)对称伸缩振动吸收峰分别出现在775和683 cm-1, 而BO3中的ν(B—O)键的振动吸收峰以及BO4四面体中的δ(B—O)的振动吸收峰分别出现在1 350和1 050 cm-1, 磁微扰的二维红外相关光谱表明B—O和V—O—V的伸缩振动对于磁场的变化具有敏感的响应峰, 热微扰的二维红外相关光谱表明B—OH, B—O和V—O—V的伸缩振动时热微扰具有敏感的响应峰。

A polyoxovanadium borate (H2dap)6H［V12B16O54(OH)4］·12H2O(dap=1,2-diaminopropane) with novel structure was hydrothermally synthesized and characterized by the single crystal X-ray diffraction. It crystallizes in triclinic system with space group Pīand unit cell parameters a=19.027(4), b=16.142(3) , c=26.679(5) , α=90°, β=101.06(3) °, γ=90°, V=8042(3) 3, Z=4, Dc=1.962 g·cm－3, μ=1.456 mm－1, F(000)=4 776, the final R1=0.062 6, wR2=0.192 7, S=1. 003, for 7 635 observed reflectionswith I>2σ(I). It is showed that the compound 1 is composed of V12B16 clusters unit and dap which is as a counter ion, and a two-dimensional layered structure is obtained by the effect of hydrogen bonding between the cluster units and dap, and between the layers via strong hydrogen bonds to form a three-dimensional supramolecular structure. The compound 1 were also characterized by IR, two-dimensional infrared (2D IR) correlation spectroscopy with magnetic and thermal perturbation, UV/Vis DRS spectra. The relationship between the structure and spectroscopy properties was discussed. The IR spectrum showed that the antisymmetric stretching vibration absorption peak νas(V—Oμ) and symmetric stretching vibration absorption peaks νs(V—Oμ) appeared at 775 and 683 cm-1 respectively, whereas the vibration absorption peak in ν(B—O) of BO3 and the vibration absorption peak in ν(B—O) of BO4 appeared at 1 350 and 1 050 cm-1 respectively. The response of the stretching vibrations of B—O and V—O was detected in the 2D IR correlation spectra with magentic perturba-tion. In addition, the response of the stretching vibrations of B—OH, B—O and V—O—V was detected in the 2D IR correlation spectra with thermal perturbation.