Visualizing the alignment of lone pair electrons in La3AsS5Br2 and La5As2S9Cl3 to form an acentric or centrosymmetric structure

文献情報

出版日 2023-10-23

DOI 10.1039/D3CE00834G

インパクトファクター 3.545

著者

Andrea Cicirello, Andrew Swindle, Jian Wang

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要旨

Acentric structures host numerous important applications such as second harmonic generation, nonreciprocal responses, etc. In this work, a heteroanionic system of La3AsS5Br2 and La5As2S9Cl3 exhibits a good example of how the alignment of lone pair electrons affects crystal structure. Noncentrosymmetric (NCS) chalcohalide La3AsS5Br2, isostructural to Pr3AsS5Cl2, and centrosymmetric chalcohalide La5As2S9Cl3 were successfully synthesized by a salt flux growth method. Crystal structures were determined by single crystal X-ray diffraction. Both compounds contain trigonal pyramidal [AsS3] units with stereochemically active lone pairs in As3+, aligning in the same direction in La3AsS5Br2 and in opposite directions in La5As2S9Cl3, which account for their acentric crystal structure and centrosymmetric structure, respectively. Electron localization function (ELF) calculations confirmed that the alignment of the [AsS3] motifs contributes to the acentric nature of La3AsS5Br2. La3AsS5Br2 is predicated to be an indirect bandgap semiconductor by theory calculations with a bandgap of 2.27 eV, which is verified by UV-Vis spectroscopy measurements to be 2.8(1) eV. The acentric structural nature of La3AsS5Br2 was demonstrated by a moderate second harmonic generation (SHG) response of 0.23× AgGaS2, where La5As2S9Cl3 exhibited no response under the same conditions.

掲載誌

CrystEngComm

CiteScore: 5.5

自己引用率: 7.7%

年間論文数: 643

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