Pei Shao-Min, Zhang Ming-Shu, Wu Fan, Guo Yan, Jiang Xiao-Ming, Liu Bin-Wen, Guo Guo-Cong
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences Fuzhou Fujian 350002 P. R. China
Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China Fuzhou Fujian 350108 P. R. China.
Chem Sci. 2024 Jul 31;15(34):13753-13759. doi: 10.1039/d4sc04018j. eCollection 2024 Aug 28.
Metals containing d-orbitals are typically characterized by strong deformation and polarization, yet they tend to induce narrow bandgaps that render them little-appreciated by high-power nonlinear optical (NLO) crystals. Incorporating highly electropositive polycations into d-orbital-containing chalcogenides to modify them into salt-inclusion chalcogenides (SICs) that are competitive in NLO materials, is a viable solution to this predicament. In the present work, two isostructural SICs [KCl][MGaS] (M = Mn, 1; Hg, 2) are successfully synthesized by the high-temperature molten-salt growth method. Both compounds demonstrate commendable second-harmonic-generation (SHG) responses (0.6-1.0 × AgGaS @1910 nm), which can be attributed to their well-designed [MGaS] anionic frameworks; and compound 2 exhibits the widest optical bandgap (3.41 eV) among the Hg-based NLO chalcogenides. Also, an interesting dual-band photoluminescence emission centered at ∼650 and ∼718 nm is detected in 1 at 77 K, with long lifetimes of 0.94 and 1.35 ms, respectively.
含有d轨道的金属通常具有强烈的变形和极化特性，但它们往往会诱导出窄带隙，这使得它们在高功率非线性光学（NLO）晶体中不太受重视。将高电正性的聚阳离子引入含d轨道的硫属化物中，将其改性为在NLO材料中具有竞争力的盐包合物硫属化物（SIC），是解决这一困境的可行方案。在本工作中，通过高温熔盐生长法成功合成了两种同构的SIC [KCl][MGaS]（M = Mn，1；Hg，2）。两种化合物均表现出值得称赞的二次谐波产生（SHG）响应（0.6 - 1.0×AgGaS @1910 nm），这可归因于其精心设计的[MGaS]阴离子骨架；化合物2在基于汞的NLO硫属化物中表现出最宽的光学带隙（3.41 eV）。此外，在77 K下于1中检测到以650和718 nm为中心的有趣的双波段光致发光发射，其寿命分别为0.94和1.35 ms。
