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Abstract Infrared nonlinear optical (IR NLO) materials are significant in laser technology for civil and military uses. Here, we report the synthesis, structural chemistry and NLO properties of a halogen‐rich chalcohalide Sn 7 Br 10 S 2 . Its noncentrosymmetric (NCS, P 6 3 ) structure can be considered as partially aliovalent anion substitution of SnBr 2 ( P 6 3 / m ) induced centrosymmetric (CS) to NCS structural transformation. The 3 D ∞ Sn(1) 6 Sn(2) 6 Br 6 X 6 6− (X=Br/S) channel framework consists of Sn(1)BrX 2 and Sn(2)X 3 trigonal pyramids. It exhibits excellent NLO performance, including a strong phase‐matchable NLO response of 1.5 × AgGaS 2 and high laser‐induced damage threshold of 6.3 × AgGaS 2 .Investigation of the structure–NLO performance relationship confirms that the effective arrangement of Sn(1)BrX 2 and Sn(2)X 3 units predominantly contributes to the large SHG response. These results indicate Sn 7 Br 10 S 2 is a potential IR NLO candidate and provides a new feasible system for promising NLO materials.
Li et al. (Fri,) studied this question.