Ln3Pb3(IO3)13(μ3-O)（Ln = La - Nd）：含两种孤对阳离子的新型二阶非线性光学材料

Ln3Pb3(IO3)13(mu3-O) (Ln = La-Nd): new types of second-order nonlinear optical materials containing two types of lone pair cations.

作者信息

Hu Ting, Qin Li, Kong Fang, Zhou Yong, Mao Jiang-Gao

机构信息

State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.

出版信息

Inorg Chem. 2009 Mar 2;48(5):2193-9. doi: 10.1021/ic8022375.

DOI:10.1021/ic8022375

PMID:19235978

Abstract

Hydrothermal reactions of lanthanide oxide, lead chloride, I(2)O(5), and H(2)O at 200 degrees C led to four novel quaternary compounds, namely, Ln(3)Pb(3)(IO(3))(13)(mu(3)-O) (Ln = La-Nd). They are isostructural, and their structures feature a complicated 3D network composed of LaO(9) and PbO(6) polyhedra interconnected by asymmetric IO(3) groups. Ln(3)Pb(3)(IO(3))(13)(mu(3)-O) (Ln = La, Pr, Nd) display moderate second harmonic generation efficiencies of about 2.0, 1.0, and 0.8 times the value of KH(2)PO(4), respectively. These compounds are thermally stable up to 520 degrees C. Luminescence measurements indicate that Ln(3)Pb(3)(IO(3))(13)(mu(3)-O) (Ln = Ce, Pr, Nd) exhibit strong emission bands in the visible or near IR region. Magnetic studies indicate that there exist significant antiferromagnetic interactions between magnetic centers in Ln(3)Pb(3)(IO(3))(13)(mu(3)-O) (Ln = Pr, Nd).

摘要

镧系氧化物、氯化铅、五氧化二碘和水在200℃下进行水热反应，生成了四种新型的四元化合物，即Ln₃Pb₃(IO₃)₁₃(μ₃ - O)（Ln = La - Nd）。它们具有相同的晶体结构，其结构的特点是由LaO₉和PbO₆多面体通过不对称的IO₃基团相互连接形成复杂的三维网络。Ln₃Pb₃(IO₃)₁₃(μ₃ - O)（Ln = La、Pr、Nd）的二次谐波产生效率适中，分别约为磷酸二氢钾（KH₂PO₄）的2.0倍、1.0倍和0.8倍。这些化合物在高达520℃的温度下热稳定性良好。发光测量表明，Ln₃Pb₃(IO₃)₁₃(μ₃ - O)（Ln = Ce、Pr、Nd）在可见光或近红外区域表现出强发射带。磁性研究表明，在Ln₃Pb₃(IO₃)₁₃(μ₃ - O)（Ln = Pr、Nd）中，磁性中心之间存在显著的反铁磁相互作用。