Department of Chemistry, University of Houston, Houston, Texas 77204, United States.
Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States.
Inorg Chem. 2023 Feb 13;62(6):2942-2950. doi: 10.1021/acs.inorgchem.2c04450. Epub 2023 Jan 30.
We report the synthesis and optical properties of noncentrosymmetric (NCS) γCsIO that was obtained through IO polyhedral rearrangements from centrosymmetric (CS) β-CsIO. Trifluoroacetic acid (TFA) acts as a structure-directing agent and plays a key role in the synthesis. It is suggested that the function of TFA is to promote rearrangement reactions found in the organic synthesis of stereoisomers. γCsIO crystallizes in the NCS monoclinic space group 2 (No. 4) and exhibits a strong second-harmonic-generation (SHG) response of 5.0 × KDP (KHPO) under 1064 nm laser radiation. Additional SHG experiments indicate that the material is type I phase matchable. First-principles calculations show that SHG intensity mainly comes from its , , and SHG tensor components. The synthetic strategy of discovering γCsIO provides a new way for designing novel NCS SHG materials.
我们报告了非中心对称（NCS）γCsIO 的合成和光学性质，γCsIO 是通过中心对称（CS）β-CsIO 的 IO 多面体重排获得的。三氟乙酸（TFA）作为结构导向剂，在合成中起着关键作用。有人认为，TFA 的作用是促进在立体异构体的有机合成中发现的重排反应。γCsIO 结晶于 NCS 单斜空间群 2（No.4），在 1064nm 激光辐射下表现出 5.0×KDP（KHPO）的强二次谐波产生（SHG）响应。额外的 SHG 实验表明，该材料是Ⅰ型相位匹配的。第一性原理计算表明，SHG 强度主要来自其 、 、 和 SHG 张量分量。发现 γCsIO 的合成策略为设计新型 NCS SHG 材料提供了一种新方法。
