Series of SHG Materials Based on Lanthanide Borate Acetate Mixed Anion Compounds
Series of SHG Materials Based on Lanthanide Borate Acetate Mixed Anion Compounds
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基于镧系硼酸醋酸盐混合阴离子化合物的倍频材料系列
DOI：
10.1021/acs.inorgchem.5b01126
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发表时间：
2015
影响因子：
4.6
通讯作者：
Mao Jiang-Gao
中科院分区：
文献类型：
--
作者：
Yang Hui;Hu Chun-Li;Xu Xiang;Mao Jiang-Gao
在水热条件下合成了第一个镧系硼酸-乙酸混合阴离子化合物Ln_2（CH_3CO_2）_2[B_5 O_9（OH）]·H_2 O（Ln = La_1; Ce_2; Pr_3）。这些化合物是同构的，并且在极性空间群Cc中结晶。它们显示出独特的三维（3D）框架，由乙酸根阴离子进一步装饰的镧系硼酸盐的3D网络构建。硼酸根阴离子在平面上呈现出一个二维层，具有大的9元环（MR），这些MR被镧系元素（III）离子填充到{Ln[B5 O 9（OH）]}−二维层中。相邻的{Ln[B5 O 9（OH）]}−层由剩余的镧系元素（III）离子桥接，形成镧系元素硼酸盐的3D网络。在500 K加热下，Ln 2（CH 3CO 2）2[B5 O 9（OH）]·H2O（Ln = La 1; Ce 2; Pr 3）可转变为Ln 2（CH 3CO 2）2[B5 O 9（OH）]（Ln = La 4; Ce 5; Pr 6）。化合物1 - 4显示中等的SHG信号，分别为KH_2 PO_4的约2.0、1.0、1.4和2.5倍，并且它们是相位匹配的。它们的倍频响应主要来自于不对称硼酸根团簇和π共轭CH_3COO-阴离子的协同极化效应。
The first examples of lanthanide borate–acetate mixed anion compounds, namely, Ln2(CH3CO2)2[B5O9(OH)]·H2O (Ln = La1; Ce2; Pr3), were synthesized under hydrothermal conditions. These compounds are isostructural and crystallize in polar space groupCc. They display a unique three-dimensional (3D) framework built by a 3D network of lanthanide borate further decorated by acetate anions. The borate anion exhibits a 2D layer in theacplane with large 9-member rings (MRs) which are filled by lanthanide(III) ions into a {Ln[B5O9(OH)]}−2D layer. Adjacent {Ln[B5O9(OH)]}−layers are bridged by remaining lanthanide (III) ions to form a 3D network of lanthanide borate. It is noteworthy that Ln2(CH3CO2)2[B5O9(OH)]·H2O (Ln = La1; Ce2; Pr3) can be changed into Ln2(CH3CO2)2[B5O9(OH)] (Ln = La4; Ce5; Pr6) under heating at 500 K. Compounds1–4display moderate SHG signals of about 2.0, 1.0, 1.4, and 2.5 times that of KH2PO4, respectively, and they are phase matchable. Their SHG responses mainly arise from the synergistic polarization effects of both asymmetric borate clusters and π-conjugated CH3COO–anions.