单独一对
化学
极化率
结晶学
非线性光学
八面体
卤化物
晶体结构
立体化学
计算化学
无机化学
分子
非线性系统
物理
有机化学
量子力学
作者
Ying‐Jie Jia,Xingyu Zhang,Yi-Gang Chen,Xingxing Jiang,Jia-Neng Song,Zheshuai Lin,Xian‐Ming Zhang
出处
期刊:Inorganic Chemistry
[American Chemical Society]
日期:2022-09-19
卷期号:61 (39): 15368-15376
被引量:28
标识
DOI:10.1021/acs.inorgchem.2c01802
摘要
Stereochemically active lone-pair (SCALP) cations are one attractive type of nonlinear optical (NLO)-active units because of their large microcosmic polarizability and anisotropy. Currently, the single and/or dual lone-pair cation-based noncentrosymmetric (NCS) oxides have been extensively investigated and verified to be one class of outstanding NLO materials. From the perspective of function optimization, the integration of three kinds of SCALP cations into one crystal may synergistically improve the NLO properties, which is greatly expected but unexplored to date. Herein, by introducing flexible metal halide bonds to guarantee the stereochemical activity and overcome the energetically favorable antiparallel arrangements of lone-pair cations, the first type of three lone-pair-cation (Pb2+, Bi3+, and Se4+)-coexisting NCS oxides PbBi(SeO3)2F (I) and Pb2Bi(SeO3)2Cl3 (II) was obtained. As expected, both compounds show outstanding NLO properties, such as the strong second-harmonic-generation signal (10.5× and 13.5 × KDP), large birefringence (0.103 and 0.186), relatively wide energy band gaps (3.75 and 3.45 eV), and good physicochemical stability. Theoretical calculations demonstrated the effect of three lone-pair-cation-based polyhedra and the halide anion on NLO properties.
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