Wei Qi, Wang Kui, He Chao, Wei Li, Li Xiao-Fei, Zhang Shuo, An Xing-Tao, Li Jin-Hua, Wang Guo-Ming
College of Chemistry and Chemical Engineering, Qingdao University, Qingdao, Shandong 266071, P. R. China.
College of Science, Hebei University of Science and Technology Shijiazhuang, Hebei 050018, P. R. China.
Inorg Chem. 2021 Aug 2;60(15):11648-11654. doi: 10.1021/acs.inorgchem.1c01653. Epub 2021 Jul 21.
Introducing stereochemically active lone-pair Sb cations into sulfates, two three-dimensional (3D) antimony-sulfates, SbOSO () and SbO(SO)(OH) (), were achieved under moderate hydrothermal conditions. Both structures are constructed by tetranuclear-{Sb}-clusters-based layers and SO tetrahedra. However, owing to the different packing patterns of the layers, they display different characteristics: exhibits a centrosymmetric structure while possesses a noncentrosymmetric structure. UV-vis spectra show that they possess wide band gaps. SbO(SO)(OH) is nonlinear optical (NLO) active with a second-harmonic generation (SHG) response of ∼1.2 times of KHPO, together with the phase-matchable capacity, endowing it a promising UV NLO material. The first-principle calculations were performed to elucidate the structure-property relationships. The results indicate that the lone pair stereoactivity of Sb provides the large contribution to the macroscopic SHG effect.
通过在硫酸盐中引入具有立体化学活性的孤对锑阳离子，在温和水热条件下成功合成了两种三维（3D）锑硫酸盐，即SbOSO（ ）和SbO(SO)(OH)（ ）。两种结构均由基于四核-{Sb}-簇的层和SO四面体构建而成。然而，由于层的堆积方式不同，它们表现出不同的特性： 具有中心对称结构，而 具有非中心对称结构。紫外可见光谱表明它们具有宽带隙。SbO(SO)(OH)具有非线性光学（NLO）活性，其二次谐波产生（SHG）响应约为KHPO的1.2倍，同时具有相位匹配能力，使其成为一种有前途的紫外NLO材料。进行了第一性原理计算以阐明结构-性能关系。结果表明，Sb的孤对立体活性对宏观SHG效应有很大贡献。
