Shui Qirui, Fu Ruibiao, Tang Hongxin, Fang Yuanbin, Ma Zuju, Wu Xintao
College of Chemical Engineering, Fuzhou University, Fuzhou, Fujian 350116, People's Republic of China.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, People's Republic of China.
Inorg Chem. 2021 Apr 5;60(7):5290-5296. doi: 10.1021/acs.inorgchem.1c00264. Epub 2021 Mar 17.
The substitution of alkali metal cation or halogen anion based on nonlinear crystals is an effective strategy to exploit new optical materials. The strategy has been successfully expanded to discover two new lead halides, RbPb(CHCOO)X (X = Br, Cl). The substitution of the Cs cation with a Rb cation can not only increase the local dipole moment of the distorted [PbBrO] polyhedron but also reduce the cell unit, resulting in a large net macroscopic polarization. Therefore, RbPb(CHCOO)Br possesses a strong second-harmonic generation (SHG) response (6 × KDP) and a large birefringence (0.18@1064 nm). Furthermore, by the substitution of the Br anion with a Cl anion, RbPb(CHCOO)Cl exhibits a high laser damage threshold (LDT, 84 × AgGaS) and a short UV cutoff edge of 287 nm, as well as moderate SHG response (3 × KDP) and birefringence (0.11@1064 nm). Detailed theory calculations elucidate the origin of the linear and nonlinear optical properties of these compounds.
基于非线性晶体的碱金属阳离子或卤素阴离子取代是开发新型光学材料的有效策略。该策略已成功扩展，发现了两种新型卤化铅，即RbPb(CHCOO)X（X = Br、Cl）。用铷阳离子取代铯阳离子不仅可以增加畸变的[PbBrO]多面体的局部偶极矩，还能减小晶胞单元，从而产生较大的净宏观极化。因此，RbPb(CHCOO)Br具有很强的二次谐波产生（SHG）响应（6×KDP）和较大的双折射（在1064 nm处为0.18）。此外，通过用氯阴离子取代溴阴离子，RbPb(CHCOO)Cl表现出高激光损伤阈值（LDT，84×AgGaS）和287 nm的短紫外截止边缘，以及适度的SHG响应（3×KDP）和双折射（在1064 nm处为0.11）。详细的理论计算阐明了这些化合物线性和非线性光学性质的起源。
