PbBi(SeO3)2F 和 Pb2Bi(SeO3)2Cl3：三种立体化学活性孤对阳离子共存，表现出优异的非线性光学性能,Inorganic Chemistry

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PbBi(SeO3)2F 和 Pb2Bi(SeO3)2Cl3：三种立体化学活性孤对阳离子共存，表现出优异的非线性光学性能
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2022-09-19 , DOI: 10.1021/acs.inorgchem.2c01802
Ying-Jie Jia ₁ , Xingyu Zhang ₂ , Yi-Gang Chen ₁ , Xingxing Jiang ₂ , Jia-Neng Song ₁ , Zheshuai Lin ₂ , Xian-Ming Zhang _{1,

3}

Affiliation

立体化学活性孤对电子（SCALP）阳离子因其较大的微观极化率和各向异性而成为一种有吸引力的非线性光学（NLO）活性单元。目前，单和/或双孤对阳离子非中心对称（NCS）氧化物已被广泛研究并验证为一类出色的非线性光学材料。从功能优化的角度来看，将三种SCALP阳离子集成到一个晶体中可以协同提高NLO性能，这是人们寄予厚望但迄今为止尚未探索的。在此，通过引入柔性金属卤化物键来保证立体化学活性并克服孤对阳离子能量上有利的反平行排列，第一类三孤对阳离子（Pb 2+ 、^Bi 3+^和Se ⁴⁺）得到共存的NCS氧化物PbBi(SeO ₃ ) ₂ F( I )和Pb ₂ Bi(SeO ₃ ) ₂ Cl ₃ ( II )。正如预期的那样，这两种化合物都表现出出色的非线性光学特性，例如强的二次谐波产生信号（10.5×和13.5×KDP）、大的双折射（0.103和0.186）、相对较宽的能带隙（3.75和3.45 eV）以及理化稳定性好。理论计算证明了三种孤对阳离子多面体和卤化物阴离子对非线性光学性质的影响。

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PbBi(SeO3)2F and Pb2Bi(SeO3)2Cl3: Coexistence of Three Kinds of Stereochemically Active Lone-Pair Cations Exhibiting Excellent Nonlinear Optical Properties

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.

更新日期：2022-09-19

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