两种新型Sn2 + -W6 +氧化物Sn2WO5和Sn3WO6的合成、结构、表征及计算

Synthesis, structure, characterization, and calculations of two new Sn2+ -W6+-oxides, Sn2WO5 and Sn3WO6.

作者信息

Chang Hong Young, Ok Kang Min, Kim Jun Ho, Halasyamani P Shiv, Stoltzfus Matthew, Woodward Patrick

机构信息

Department of Chemistry and Center for Materials Chemistry, 136 Fleming Building, University of Houston, Houston, TX 77204-5003, USA.

出版信息

Inorg Chem. 2007 Aug 20;46(17):7005-11. doi: 10.1021/ic700740m. Epub 2007 Jul 21.

DOI:10.1021/ic700740m

PMID:17658875

Abstract

Two new Sn2+-W6+-oxides, Sn2WO5 and Sn3WO6, have been synthesized hydrothermally, and their structures have been determined by single-crystal X-ray diffraction methods. Both materials exhibit layered structural topologies consisting of two edge-shared WO6 octahedra connected to SnO3 and SnO4 polyhedra. Both the W6+ and Sn2+ cations are in locally asymmetric coordination environments attributable to second-order Jahn-Teller effects. Infrared and Raman spectroscopy, UV-vis diffuse reflectance spectroscopy, and thermogravimetric analysis were also performed on the reported materials. Theoretical calculations using the tight binding linear muffin tin orbital method agree with the observed electronic properties of these materials and indicate that the stereoactive lone pair on the Sn2+ is similar for both materials. Crystal data: Sn2WO5, monoclinic, space group P21/n (No. 14), a = 7.994(2) A, b = 13.712(4) A, c = 10.383(3) A, beta = 110.507(3) degrees , V = 1066.0(5) A3, and Z = 4; Sn3WO6, monoclinic, C2/c (No. 15), a = 12.758(3) A, b = 8.0838(16) A, c = 13.865(3) A, beta = 112.49(3) degrees , V = 1321.2(5) A3, and Z = 8.

摘要

通过水热法合成了两种新型的Sn2+-W6+氧化物Sn2WO5和Sn3WO6，并采用单晶X射线衍射方法确定了它们的结构。这两种材料均呈现出层状结构拓扑，由两个与SnO3和SnO4多面体相连的共边WO6八面体组成。W6+和Sn2+阳离子均处于由于二阶 Jahn-Teller 效应导致的局部不对称配位环境中。还对所报道的材料进行了红外光谱、拉曼光谱、紫外-可见漫反射光谱和热重分析。使用紧束缚线性 muffin 锡轨道方法进行的理论计算与这些材料观察到的电子性质相符，并表明两种材料中Sn2+上的立体活性孤对相似。晶体数据：Sn2WO5，单斜晶系，空间群P21/n（编号14），a = 7.994(2) Å，b = 13.712(4) Å，c = 10.383(3) Å，β = 110.507(3)°，V = 1066.0(5) Å3，Z = 4；Sn3WO6，单斜晶系，C2/c（编号15），a = 12.758(3) Å，b = 8.0838(16) Å，c = 13.865(3) Å，β = 112.49(3)°，V = 1321.2(5) Å3，Z = 8。