State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, PR China.
Inorg Chem. 2010 Dec 20;49(24):11627-36. doi: 10.1021/ic1020737. Epub 2010 Nov 23.
Six new novel alkaline-earth metal vanadium(V) or vanadium(IV) selenites and tellurites, namely, Sr(2)(VO)(3)(SeO(3))(5), Sr(V(2)O(5))(TeO(3)), Sr(2)(V(2)O(5))(2)(TeO(3))(2)(H(2)O), Ba(3)(VO(2))(2)(SeO(3))(4), Ba(2)(VO(3))Te(4)O(9)(OH), and Ba(2)V(2)O(5)(Te(2)O(6)), have been prepared and structurally characterized by single crystal X-ray diffraction analyses. These compounds exhibit six different anionic structures ranging from zero-dimensional (0D) cluster to three-dimensional (3D) network. Sr(2)(VO)(3)(SeO(3))(5) features a 3D anionic framework composed of VO(6) octahedra that are bridged by SeO(3) polyhedra. The oxidation state of the vanadium cation is +4 because of the partial reduction of V(2)O(5) by SeO(2) at high temperature. Ba(3)(VO(2))(2)(SeO(3))(4) features a 0D (VO(2))(SeO(3))(2) anion. Sr(V(2)O(5))(TeO(3)) displays a unique 1D vanadium(V) tellurite chain composed of V(2)O(8) and V(2)O(7) units connected by tellurite groups, forming 4- and 10-MRs, whereas Sr(2)(V(2)O(5))(2)(TeO(3))(2)(H(2)O) exhibits a 2D layer consisting of [V(4)O(14)] tetramers interconnected by bridging TeO(3)(2-) anions with the Sr(2+) and water molecules located at the interlayer space. Ba(2)(VO(3))Te(4)O(9)(OH) exhibits a one-dimensional (1D) vanadium tellurite chain composed of a novel 1D Te(4)O(9)(OH) chain further decorated by VO(4) tetrahedra. Ba(2)V(2)O(5)(Te(2)O(6)) also features a 1D vanadium(V) tellurites chain in which neighboring VO(4) tetrahedra are bridged by Te(2)O(6) dimers. The existence of V(4+) ions in Sr(2)(VO)(3)(SeO(3))(5) is also confirmed by magnetic measurements. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory (DFT) methods indicate that all six compounds are wide-band gap semiconductors.
六种新型碱土金属钒(V)或钒(IV)硒酸盐和碲酸盐，即 Sr(2)(VO)(3)(SeO(3))(5)、Sr(V(2)O(5))(TeO(3))、Sr(2)(V(2)O(5))(2)(TeO(3))(2)(H(2)O)、Ba(3)(VO(2))(2)(SeO(3))(4)、Ba(2)(VO(3))Te(4)O(9)(OH)和 Ba(2)V(2)O(5)(Te(2)O(6))，已通过单晶 X 射线衍射分析进行了制备和结构表征。这些化合物表现出从零维 (0D) 簇到三维 (3D) 网络的六种不同的阴离子结构。Sr(2)(VO)(3)(SeO(3))(5)具有由 VO(6)八面体组成的 3D 阴离子骨架，这些八面体由 SeO(3)多面体桥接。由于 V(2)O(5)在高温下被 SeO(2)部分还原，因此钒阳离子的氧化态为+4。Ba(3)(VO(2))(2)(SeO(3))(4)具有 0D (VO(2))(SeO(3))(2)阴离子。Sr(V(2)O(5))(TeO(3))呈现出独特的一维钒(V)碲酸盐链，由 V(2)O(8)和 V(2)O(7)单元通过碲酸盐基团连接而成，形成 4-和 10-MRs，而 Sr(2)(V(2)O(5))(2)(TeO(3))(2)(H(2)O)则具有由 [V(4)O(14)]四聚体组成的二维层，通过桥连 TeO(3)(2-)阴离子与 Sr(2+)和水分子连接，位于层间空间。Ba(2)(VO(3))Te(4)O(9)(OH)呈现出由新型一维Te(4)O(9)(OH)链进一步修饰的一维钒碲酸盐链，该链由 VO(4)四面体组成。Ba(2)V(2)O(5)(Te(2)O(6))也具有一维钒(V)碲酸盐链，其中相邻的 VO(4)四面体由Te(2)O(6)二聚体桥接。Sr(2)(VO)(3)(SeO(3))(5)中 V(4+)离子的存在也通过磁性测量得到证实。基于密度泛函理论 (DFT) 方法的光学漫反射谱测量和电子结构计算的结果表明，所有六种化合物都是宽带隙半导体。
