Wang Weiyi, Wang Xinyue, Xu Lu, Zhang Die, Xue Jiale, Wang Shuyao, Dong Xuehua, Cao Liling, Huang Ling, Zou Guohong
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610066, P. R. China.
College of Chemistry, Sichuan University, Chengdu 610065, P. R. China.
Inorg Chem. 2023 Aug 14;62(32):13148-13155. doi: 10.1021/acs.inorgchem.3c02175. Epub 2023 Aug 2.
Herein, we have successfully synthesized two rubidium antimony (III) oxalates, namely, RbSb(CO)(HO) and RbSb(CO)F, utilizing a low-temperature hydrothermal method. These two compounds share a similar chemical composition, consisting of Sb cations with active lone pair electrons, alkali metal Rb ions, and planar π-conjugated CO anions. However, they exhibit different symmetries, RbSb(CO)(HO) is centrosymmetric (CS), while RbSb(CO)F is noncentrosymmetric (NCS), which should be caused by the presence of F ions. Notably, the NCS compound, RbSb(CO)F, demonstrates a moderate second-harmonic generation (SHG) response, approximately 1.3 times that of KHPO (KDP), and exhibits a large birefringence of 0.09 at 546 nm. These characteristics indicate that RbSb(CO)F holds promising potential as a nonlinear optical material for ultraviolet (UV) applications. Detailed structural analysis and theoretical calculations confirm that the excellent optical properties arise from the synergistic effects between Sb cations with SCALP and planar π-conjugated [CO] groups.
在此，我们利用低温水热法成功合成了两种铷锑（III）草酸盐，即RbSb(C₂O₄)(H₂O)和RbSb(C₂O₄)F。这两种化合物具有相似的化学组成，由具有活性孤对电子的Sb阳离子、碱金属Rb离子和平面π共轭C₂O₄²⁻阴离子组成。然而，它们表现出不同的对称性，RbSb(C₂O₄)(H₂O)是中心对称（CS）的，而RbSb(C₂O₄)F是非中心对称（NCS）的，这应该是由F离子的存在导致的。值得注意的是，非中心对称化合物RbSb(C₂O₄)F表现出中等的二次谐波产生（SHG）响应，约为KH₂PO₄（KDP）的1.3倍，并且在546 nm处表现出0.09的大双折射。这些特性表明RbSb(C₂O₄)F作为一种用于紫外（UV）应用的非线性光学材料具有广阔的前景。详细的结构分析和理论计算证实，优异的光学性能源于具有孤对电子的Sb阳离子和平面π共轭[C₂O₄]基团之间的协同效应。
