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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=1.962g·cm-3,μ=1.456mm-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683cm-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 050cm-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 novel structure of polyoxaboric compound (H2dap) 6H [V12B16O54 (OH) 4] · 12H2O (dap = 1,2-diaminopropane) was synthesized by hydrothermal method. Single crystal X-ray (4), b = 16.142 (3), c = 26.679 (5), α = 90 ° and β = 101.06, respectively. The results show that compound 1 belongs to the monoclinic space group C2 / (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 The independent diffraction spot [I> 2σ (I)] can be observed. The final structure is refined to the deviation factor R1 = 0.0626, wR2 = 0.192 7, S = 1.003. The structure of the compound mainly consists of V12B16 cluster unit and 1,2-propanediamine as a counter ion, and the cluster units are connected by the action of strong hydrogen bond N-H ... O and weak hydrogen bond C-H ... O The two-dimensional layered structure, layer and layer is also connected by the role of hydrogen bonds into a three-dimensional supramolecular structure. In addition, the compound 1 was characterized by infrared spectroscopy, two-dimensional infrared correlation spectroscopy under magnetic perturbation, two-dimensional infrared correlation spectroscopy under thermal perturbation and ultraviolet-visible solid diffuse reflectance spectroscopy. The structure and The relationship between spectral properties. Infrared spectra showed that the symmetrical stretching vibration absorption peaks of νas (V-Oμ) and νs (V-Oμ) appeared at 775 and 683 cm-1, respectively, while the vibrational absorption of ν (B-O) The vibrational absorption peaks of δ (B-O) in BO4 and tetrahedron of BO4 appear at 1 350 and 1 050 cm-1, respectively. The two-dimensional infrared correlation spectrum of magnetic perturbation shows the stretching vibration of B-O and V-O-V For the change of magnetic field, it has a sensitive response peak. The two-dimensional infrared correlation spectrum of thermal perturbation shows that the thermal perturbation of B-OH, B-O and V-O-V has sensitive response peak.