The polar [WO2F4]2- anion in the solid state

被引:59
作者
Heier, KR [1 ]
Norquist, AJ [1 ]
Halasyamani, PS [1 ]
Duarte, A [1 ]
Stern, CL [1 ]
Poeppelmeier, KR [1 ]
机构
[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
基金
美国国家科学基金会;
关键词
D O I
10.1021/ic980863h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The cis-[WO2F4](2-) anion is inherently acentric and contains polarizable W=O bonds, making it a good candidate for second-harmonic generation (SHG). However, the orientational disorder commonly found in crystal structures containing [WO2F4](2-) must be understood as a first step toward engineering a polar SHG material with this anion. The strategy of crystallizing the [WO2F4](2-) anion with two different cations, which was successful in ordering the related [NbOF5](2-) and cis-[MoO2F4](2-) anions, is able to order one of the two W=O bonds. Close inspection of bond lengths and anisotropic thermal ellipsoids in disordered [WO2F4](2-) compounds gives insight into disorder mechanisms and suggests strategies for eliminating orientational disorder. Crystal data: for [pyH](2)-[Cu(py)(4)(WO2F4)(2)], tetragonal, space group I4(1)22 (No. 98), with a 11.339(2) Angstrom, c = 30.489(6) Angstrom, and Z = 4; for Cu(pyz)(2)WO2F4.(pyz)(H2O) polymorph I, tetragonal, space group I4/mcm (No. 140), with a = 9.745(1) Angstrom, c = 16.565(3) Angstrom, and Z = 4; for Cu(pyz)(2)WO2F4.(pyz)(H2O) polymorph II, tetragonal, space group P4/mmm (No. 123), with a = 6.886(3) Angstrom, c = 8.300(2) Angstrom, and Z = 1.
引用
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页码:762 / 767
页数:6
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