Department of Chemistry, Chung-Ang University, 221 Heukseok-dong, Dongjak-gu, Seoul 156-756, Republic of Korea.
Inorg Chem. 2011 May 16;50(10):4473-80. doi: 10.1021/ic200135k. Epub 2011 Apr 12.
Two new quaternary mixed metal oxide materials--InVTe(2)O(8) and InVSe(2)O(8)--have been synthesized, as crystals and pure bulk powders by standard solid-state reactions using In(2)O(3), V(2)O(5), and TeO(2) (or SeO(2)) as reagents. The crystal structures of the reported materials were determined using single-crystal X-ray diffraction. InVTe(2)O(8) crystallizes in the monoclinic centrosymmetric space group P2(1)/n (No. 14), with unit-cell parameters of a = 7.8967(16) Å, b = 5.1388(10) Å, c = 16.711(3) Å, β = 94.22(3)°, and Z = 4, and InVSe(2)O(8) crystallizes in the noncentrosymmetric space group Pm (No. 6) with unit-cell parameters of a = 4.6348(9) Å, b = 6.9111(14) Å, c = 10.507(2) Å, β = 97.77(3)°, and Z = 2. While the centrosymmetric InVTe(2)O(8) shows a two-dimensional (2D) layered structure composed of InO(6) octahedra, VO(4) tetrahedra, and TeO(4) polyhedra, the noncentrosymmetric InVSe(2)O(8) exhibits a three-dimensional (3D) framework structure with distorted InO(6) octahedra, VO(5) square pyramids, and SeO(3) polyhedra. Powder second-harmonic generation (SHG) measurements on InVSe(2)O(8), using 1064-nm radiation, indicate that the material has a SHG efficiency ~30 times that of α-SiO(2). Additional SHG measurements reveal that the material is not phase-matchable (Type 1). Infrared, ultraviolet-visible light (UV-vis) diffuse reflectance, and thermogravimetric analyses for the two compounds are also presented, as are dipole moment calculations.
两种新的四元混合金属氧化物材料--InVTe(2)O(8) 和 InVSe(2)O(8)--已经通过使用 In(2)O(3)、V(2)O(5)和 TeO(2)(或 SeO(2))作为试剂的标准固态反应合成，作为晶体和纯块状粉末。所报道材料的晶体结构使用单晶 X 射线衍射确定。InVTe(2)O(8)结晶为单斜中心对称空间群 P2(1)/n(No. 14)，具有晶胞参数 a = 7.8967(16)Å，b = 5.1388(10)Å，c = 16.711(3)Å，β = 94.22(3)°和 Z = 4，而 InVSe(2)O(8)结晶为非中心对称空间群 Pm(No. 6)，具有晶胞参数 a = 4.6348(9)Å，b = 6.9111(14)Å，c = 10.507(2)Å，β = 97.77(3)°和 Z = 2。虽然中心对称的 InVTe(2)O(8)显示出由 InO(6)八面体、VO(4)四面体和 TeO(4)多面体组成的二维(2D)层状结构，但非中心对称的 InVSe(2)O(8)具有扭曲的 InO(6)八面体、VO(5)四方锥和 SeO(3)多面体的三维(3D)框架结构。使用 1064nm 辐射对 InVSe(2)O(8)的粉末二次谐波产生(SHG)测量表明，该材料的 SHG 效率约为α-SiO(2)的 30 倍。额外的 SHG 测量表明该材料不可相位匹配(Type 1)。还介绍了两种化合物的红外、紫外-可见漫反射和热重分析，以及偶极矩计算。
