Structures and properties of functional metal selenites and tellurites
Structures and properties of functional metal selenites and tellurites
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功能金属亚硒酸盐和亚碲酸盐的结构和性能
DOI：
10.1021/ic8005629
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发表时间：
2008-10-06
影响因子：
4.6
通讯作者：
Kong, Fang
中科院分区：
文献类型：
--
作者：
Mao, Jiang-Gao;Jiang, Hal-Long;Kong, Fang
金属亚硒酸盐和亚碲酸盐是一类非常重要的化合物。本文综述了过渡金属(TM)离子与过渡金属(TM)离子结合形成的过渡主族元素的DO电子构型或四面体Mo4构筑块的结构和性质。在碱或碱-eafth-d(0)Tm-Se-IV(或Te-IV)-O体系中，大多数化合物都表现出扩展的阴离子结构，由(DO)Tm阳离子的扭曲八面体和亚硒酸盐或亚硒酸盐基团组成。八面体的扭曲总是远离孤对阳离子，其中一些由于两种键极化的加合效应而表现出良好的二阶非线性光学性质。由于Ln(III)离子的高配位数，Ln-d(0)Tm-Se-IV(或Te-IV)-O体系中的大多数化合物不具有二次谐波活性，但它们在可见光或近红外区都能发出强烈的发光；在大多数情况下，DO Tm离子呈四面体构型，并与亚硒酸盐或亚碲酸盐基团很好地分开。还值得注意的是，亚硒酸根通常是孤立的，而TeOx(x=3-5)可以通过Te-O-Te桥聚合成各种离散的多核阴离子簇或扩展的结构。
Metal selenites and tellurites are a class of very important compounds. In this paper, the structures and properties of metal selenites or tellurites combining with transition-metal (TM) ions with the do electronic configuration or tetrahedral MO4 building blocks of post-transition main-group elements were reviewed. Most compounds in the alkali or alkaline-eafth-d(0) TM-Se-IV (or Te-IV)-O systems exhibit extended anionic architectures composed of distorted octahedra of (do) TM cations and tellurite or selenite groups. The distortion of the octahedron is always away from the lone-pair cation, and some of them exhibit excellent second-order nonlinear optical properties due to the adductive effects of two types of bond polarizations. Because of the high coordination number of Ln(III) ions, most of compounds in the Ln-d(0) TM-Se-IV (or Te-IV)-O systems are not second-harmonic-generation active; however, they are able to emit strong luminescence in the visible or near-IR region; also in most cases, the do TM cations are in tetrahedral geometry and are well separated from selenite or tellurite groups. It is also interesting to note that the selenite group is normally "isolated", whereas the TeOx (x = 3-5) can be polymerized into a variety of discrete polynuclear anionic clusters or extended architectures via Te-O-Te bridges.