Chen Danping, Song Zhexin, Yang Can, Wei Yaoyao, Liu Guokui, Meng Lingqiang, Wu Qi, Dang Yangyang
School of Physics and Physical Engineering, Qufu Normal University, Qufu 273165, P. R. China.
State Key Laboratory of New Textile Materials and Advanced Processing Technologies, Wuhan Textile University, Wuhan 430200, P. R. China.
Inorg Chem. 2024 Jun 3;63(22):10304-10311. doi: 10.1021/acs.inorgchem.4c00980. Epub 2024 May 23.
Organic-inorganic hybrid metal halides have unique optical and electronic properties, which are advantageous in the study of nonlinear optical materials. To investigate the effect of stereoactive lone pair electrons and the induction of organic cations on the structure of hybrid antimony(III) halides on nonlinear optics, we synthesize two noncentrosymmetric hybrid antimony(III)-based halide single crystals (TMA)SbX (TMA = NH(CH), X = Cl, Br) by a room-temperature slow evaporation method, and their single-crystal structures, phase transition, X-ray photoelectron spectroscopy, and energy-band structure calculations are studied. More importantly, second-harmonic generation results of (TMA)SbX (X = Cl, Br) are about 0.7 and 0.8 × KHPO(KDP), respectively. Interestingly, (TMA)SbCl single crystals undergo a reversible structural transition from (No. 7) at room temperature to 2/ (No. 14) at 400 K, while the (TMA)SbBr single crystals belong to the noncentrosymmetric space group 3c (No. 161), which clarifies the previous results. This work not only deepens the understanding of the role in lone pair electrons and organic cations in the structural induction in antimony-based halide perovskite materials but also provides guidance for subsequent nonlinear optical explorations.
有机-无机杂化金属卤化物具有独特的光学和电子性质，这在非线性光学材料的研究中具有优势。为了研究立体活性孤对电子和有机阳离子的诱导作用对杂化锑（III）卤化物结构在非线性光学方面的影响，我们通过室温缓慢蒸发法合成了两种非中心对称的基于锑（III）的卤化物单晶（TMA）SbX（TMA = NH(CH)，X = Cl，Br），并对它们的单晶结构、相变、X射线光电子能谱和能带结构计算进行了研究。更重要的是，（TMA）SbX（X = Cl，Br）的二次谐波产生结果分别约为0.7和0.8×KHPO（KDP）。有趣的是，（TMA）SbCl单晶在室温下从（7号）发生可逆结构转变，在400 K时转变为2/（14号），而（TMA）SbBr单晶属于非中心对称空间群3c（161号），这澄清了先前的结果。这项工作不仅加深了对孤对电子和有机阳离子在锑基卤化物钙钛矿材料结构诱导中作用的理解，也为后续的非线性光学探索提供了指导。
