Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China.
J Am Chem Soc. 2012 Feb 1;134(4):2227-35. doi: 10.1021/ja209711x. Epub 2012 Jan 24.
Novel SHG effective inorganic open-framework chalcohalides, Ba(3)AGa(5)Se(10)Cl(2) (A = Cs, Rb and K), have been synthesized by high temperature solid state reactions. These compounds crystallize in the tetragonal space group I ̅4 (No.82) with a = b = 8.7348(6) - 8.6341(7) Å, c = 15.697(3) - 15.644(2) Å, V = 1197.6(3) - 1166.2(2) Å(3) on going from Cs to K. The polar framework of (3)(∞)Ga(5)Se(10) is constructed by nonpolar GaSe(4)(5- )tetrahedron (T1) and polar supertetrahedral cluster Ga(4)Se(10)(8-) (T2) in a zinc-blende topological structure with Ba/A cations and Cl anions residing in the tunnels. Remarkably, Ba(3)CsGa(5)Se(10)Cl(2) exhibits the strongest intensity at 2.05 μm (about 100 times that of the benchmark AgGaS(2) in the particle size of 30-46 μm) among chalcogenides, halides, and chalcohalides. Furthermore, these compounds are also the first open-framework compounds with red photoluminescent emissions. The Vienna ab initio theoretical studies analyze electronic structures and linear and nonlinear optical properties.
新型 SHG 有效无机开放式卤化物 Ba(3)AGa(5)Se(10)Cl(2)（A = Cs、Rb 和 K），通过高温固相反应合成。这些化合物在四方晶系 I ̅4（No.82）中结晶，具有 a = b = 8.7348(6) - 8.6341(7) Å，c = 15.697(3) - 15.644(2) Å，V = 1197.6(3) - 1166.2(2) Å(3)，从 Cs 到 K。（3）（∞）Ga(5)Se(10)的极性骨架由非极性 GaSe(4)(5-)四面体（T1）和极性超四面体簇 Ga(4)Se(10)(8-)（T2）构建，具有闪锌矿拓扑结构，Ba/A 阳离子和 Cl 阴离子位于隧道中。值得注意的是，Ba(3)CsGa(5)Se(10)Cl(2)在 2.05μm 处表现出最强的强度（粒径为 30-46μm 的基准 AgGaS(2)的约 100 倍），在硫属化物、卤化物和卤化物中。此外，这些化合物也是具有红色光致发光发射的第一批开放式框架化合物。维也纳从头理论研究分析了电子结构和线性与非线性光学性质。
