Zou Guohong, Jo Hongil, Lim Seong-Ji, You Tae-Soo, Ok Kang Min
College of Chemistry, Sichuan University, Chengdu, 610064, P. R. China.
Department of Chemistry, Chung-Ang University, Seoul, 06974, Republic of Korea.
Angew Chem Int Ed Engl. 2018 Jul 9;57(28):8619-8622. doi: 10.1002/anie.201804354. Epub 2018 Jun 12.
A nonlinear optical (NLO) carbonatoperoxovanadate, Rb VO(O ) CO , was synthesized through a simple solution-evaporation method in phase-pure form. Single-crystal X-ray diffraction revealed that the structure of Rb VO(O ) CO consists of important noncentrosymmetric (NCS) chromophores, that is, π-delocalized (CO ) groups, a second-order Jahn-Teller (SOJT) distortive V cation, and π-localized distorted O groups, as well as charge-balancing polarizable Rb ions. The powder second-harmonic generation (SHG) measurements indicated that Rb VO(O ) CO is phase-matchable (Type I) and exhibits a remarkably strong SHG response circa 21.0 times that of potassium dihydrogen phosphate (KDP), which is the largest efficiency observed among carbonate NLO materials. First-principles calculation analysis suggests that the extremely large SHG response of Rb VO(O ) CO is attributed to the synergistic effect of the cooperation of all the constituting NCS chromophores.
通过简单的溶液蒸发法合成了一种非线性光学（NLO）碳酸过氧钒酸盐RbVO(O₂)₂CO₃，其为纯相形式。单晶X射线衍射表明，RbVO(O₂)₂CO₃的结构由重要的非中心对称（NCS）发色团组成，即π离域的(CO₃²⁻)基团、二阶 Jahn-Teller（SOJT）畸变的V阳离子和π定域的畸变O基团，以及电荷平衡的可极化Rb离子。粉末二次谐波产生（SHG）测量表明，RbVO(O₂)₂CO₃是可相位匹配的（I型），并且表现出非常强的SHG响应，约为磷酸二氢钾（KDP）的21.0倍，这是在碳酸盐NLO材料中观察到的最大效率。第一性原理计算分析表明，RbVO(O₂)₂CO₃极大的SHG响应归因于所有构成NCS发色团协同作用的协同效应。
