Cao Xue-Li, Hu Chun-Li, Kong Fang, Mao Jiang-Gao
†State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China.
‡University of the Chinese Academy of Sciences, Beijing 100039, P. R. China.
Inorg Chem. 2015 Apr 20;54(8):3875-82. doi: 10.1021/acs.inorgchem.5b00052. Epub 2015 Apr 2.
Two new cesium selenites containing TaO6 or TiO4F2 octahedra, namely, Cs(TaO2)3(SeO3)2 (1) and Cs(TiOF)3(SeO3)2 (2), have been prepared using standard high temperature solid-state method and hydrothermal reaction, respectively. Compound 1 crystallizes in P3̅m1 and features an unusual (TaO2)3(SeO3)2 sandwich-like double layer in which two Ta(1)O3(SeO3) layers are bridged by central Ta(2)O6 octahedra via corner-sharing, whereas Cs(TiOF)3(SeO3)2 with a polar space group P63mc features an interesting hexagonal tungsten oxide (HTO) layered topology and presents a strong second harmonic generation (SHG) of about 5 × KDP (KH2PO4), which is much larger than those of A(VO2)3(QO3)2 (A = K, Tl, Rb, Cs, or NH4; Q = Se, Te) with a similar HTO layered structure. Cs(TiOF)3(SeO3)2 is also type-I phase matching. The SHG of above-mentioned HTO materials can be enhanced greatly with the replacement of VO6 octahedra by TiO4F2 octahedra. Furthermore, thermal stabilities, UV-vis diffuse reflectance spectra, infrared spectra, relationship between crystal structure and SHG, and theoretical calculations were also reported.
利用标准高温固态法和水热反应分别制备了两种含TaO6或TiO4F2八面体的新型亚硒酸铯，即Cs(TaO2)3(SeO3)2 (1)和Cs(TiOF)3(SeO3)2 (2)。化合物1结晶于P3̅m1空间群，其特征是具有不寻常的(TaO2)3(SeO3)2三明治状双层结构，其中两个Ta(1)O3(SeO3)层通过中心Ta(2)O6八面体以共角方式相连；而具有极性空间群P63mc的Cs(TiOF)3(SeO3)2具有有趣的六方氧化钨(HTO)层状拓扑结构，并且呈现出约为5×KDP(KH2PO4)的强二次谐波产生(SHG)，这比具有类似HTO层状结构的A(VO2)3(QO3)2(A = K、Tl、Rb、Cs或NH4；Q = Se、Te)的二次谐波产生要大得多。Cs(TiOF)3(SeO3)2也是I型相位匹配。用TiO4F2八面体取代VO6八面体可大大增强上述HTO材料的SHG。此外，还报道了它们的热稳定性、紫外-可见漫反射光谱、红外光谱、晶体结构与SHG的关系以及理论计算结果。
