Explorations of New Second-Order Nonlinear Optical Materials in the Potassium Vanadyl Iodate System
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- 作者：Chuan-Fu Sun ; Chun-Li Hu ; Xiang Xu ; Bing-Ping Yang ; Jiang-Gao Mao
- 刊名：Journal of the American Chemical Society
- 出版年：2011
- 出版时间：April 13, 2011
- 年：2011
- 卷：133
- 期：14
- 页码：5561-5572
- 全文大小：1278K
- 年卷期：v.133,no.14(April 13, 2011)
- ISSN：1520-5126
文摘
Four new potassium vanadyl iodates based on lone-pair-containing IO3 and second-order Jahn鈭扵eller distorted VO5 or VO6 asymmetric units, namely, 伪-KVO2(IO3)2(H2O) (Pbca), 尾-KVO2(IO3)2(H2O) (P212121), K4[(VO)(IO3)5]2(HIO3)(H2O)2路H2O (P1), and K(VO)2O2(IO3)3 (Ima2) have been successfully synthesized by hydrothermal reactions. 伪-KVO2(IO3)2(H2O) and 尾-KVO2(IO3)2(H2O) exhibit two different types of 1D [VO2(IO3)2]鈭?/sup> anionic chains. Neighboring VO6 octahedra in the 伪-phase are corner-sharing into a 1D chain with the IO3 groups attached on both sides of the chain in a uni- or bidentate bridging fashion, whereas those of VO5 polyhedra in the 尾-phase are bridged by IO3 groups into a right-handed helical chain with remaining IO3 groups being grafted unidentately on both sides of the helical chain. The structure of K4[(VO)(IO3)5]2(HIO3)(H2O)2路H2O contains novel isolated [(VO)(IO3)5]2鈭?/sup> units composed of one VO6 octahedron linked to five IO3 groups and one terminal O2鈭?/sup> anion. The structure of K(VO)2O2(IO3)3 exhibits a 1D [(VO)2O2(IO3)3]鈭?/sup> chain in which neighboring VO6 octahedra are interconnected by both oxo and bridging iodate anions. Most interestingly, three of four compounds are noncentrosymmetric (NCS), and K(VO)2O2(IO3)3 displays a very strong second-harmonic generation response of about 3.6 脳 KTP, which is phase matchable. It also has high thermal stability, a wide transparent region and moderate hardness as well as an excellent growth habit. Thermal analyses and optical and ferroelectric properties as well as theoretical calculations have also been performed.