SnPQ3 (Q = S, Se, S/Se): A Series of Lone-Pair Cationic Chalcogenophosphates Exhibiting Balanced NLO Activity Originating from SnQ8 Units

Zhi-Hui Shi; Mei Yang; Wen-Dong Yao; Wenlong Liu; Sheng-Ping Guo

doi:10.1021/acs.inorgchem.1c02178

SnPQ₃ (Q = S, Se, S/Se): A Series of Lone-Pair Cationic Chalcogenophosphates Exhibiting Balanced NLO Activity Originating from SnQ₈ Units

Inorg Chem. 2021 Sep 20;60(18):14390-14398. doi: 10.1021/acs.inorgchem.1c02178. Epub 2021 Aug 31.

Authors

Zhi-Hui Shi¹, Mei Yang¹, Wen-Dong Yao¹, Wenlong Liu¹, Sheng-Ping Guo¹

Affiliation

¹ School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002, People's Republic of China.

PMID: 34464110
DOI: 10.1021/acs.inorgchem.1c02178

Abstract

Two chalcogenophosphates, SnPS_2.86Se_0.14 (1) and SnPSe₃ (2), are isostructural and crystallize in the monoclinic noncentrosymmetric space group Pn. Their three-dimensional (3D) structures are constructed by [Sn(1)Q₈] hendecahedra and [Sn(2)Q₈] dodecahedra by sharing Q vertices and edges, leaving cavities for isolated [P₂Q₆] (Q = S/Se, Se) dimers. A second-harmonic-generation (SHG) measurement indicates that 1 is phase-matchable with a response of approximately 1.2 × AgGaS₂ (AGS), which is verified by the theoretical calculation result. The powder sample of 1 exhibits a high laser-induced damage threshold of 3.9 × AGS. For comparison, the known SnPS₃ (3) was also synthesized and evaluated using the same method. The chemical composition-NLO performance relationship of 1-3 is also discussed. Dipole moment calculation results suggest that [SnQ₈] polyhedra make the main contribution to their excellent nonlinear optical (NLO) performance.