Liu Youchao, Liu Xiaomeng, Liu Shuai, Ding Qingran, Li Yanqiang, Li Lina, Zhao Sangen, Lin Zheshuai, Luo Junhua, Hong Maochun
State Key Laboratory of Structural Chemistry, Fujian institute of Research on the Structure of Matter, Chinese Academy of Sciences, 155 Yangqiao Road West, Fuzhou, Fujian, 350002, P. R. China.
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
Angew Chem Int Ed Engl. 2020 May 11;59(20):7793-7796. doi: 10.1002/anie.202001042. Epub 2020 Mar 6.
Antimony(III) borates with a stereochemical active lone pair remained unknown, although the first antimony borate was reported more than twenty years ago. Now, the first antimony(III) borate in a closed system is successfully synthesized, namely SbB O . Remarkably, SbB O not only exhibits an exceptional linear optical response, that is, birefringence of Δn=0.290 at the wavelength of 546 nm, which is the largest among borates, but also has a strong nonlinear optical response of 3.5 times larger than the benchmark KH PO , exceeding those of most borates. Theoretical calculations reveal that the coexistence of strong linear and nonlinear optical responses in SbB O should be attributable to the synergistic effect of π-conjugated B-O anionic groups and Sb with stereochemically active lone pair. This work provides a new class of optical bi-functional materials with potential prospects in integrated optical devices.
尽管二十多年前就报道了首例硼酸锑，但含有立体化学活性孤对电子的三价锑硼酸盐一直未知。现在，在封闭体系中成功合成了首例三价锑硼酸盐，即SbBO 。值得注意的是，SbBO不仅表现出异常的线性光学响应，即在546 nm波长处的双折射Δn = 0.290，这在硼酸盐中是最大的，而且还具有比基准KHPO大3.5倍的强非线性光学响应，超过了大多数硼酸盐。理论计算表明，SbBO中强线性和非线性光学响应的共存应归因于π共轭B - O阴离子基团和具有立体化学活性孤对电子的Sb的协同效应。这项工作提供了一类新型的光学双功能材料，在集成光学器件中具有潜在的应用前景。
