Sn7Br10S2: The First Ternary Halogen‐Rich Chalcohalide Exhibiting a Chiral Structure and Pronounced Nonlinear Optical Properties

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 Sn7Br10S2. Its noncentrosymmetric (NCS, P63) structure can be considered as partially aliovalent anion substitution of SnBr2 (P63/m) induced centrosymmetric (CS) to NCS structural transformation. The 3D ∞[Sn(1)6Sn(2)6Br6X6]6− (X=Br/S) channel framework consists of Sn(1)BrX2 and Sn(2)X3 trigonal pyramids. It exhibits excellent NLO performance, including a strong phase‐matchable NLO response of 1.5 × AgGaS2and high laser‐induced damage threshold of 6.3 × AgGaS2.Investigation of the structure–NLO performance relationship confirms that the effective arrangement of Sn(1)BrX2 and Sn(2)X3 units predominantly contributes to the large SHG response. These results indicate Sn7Br10S2 is a potential IR NLO candidate and provides a new feasible system for promising NLO materials. The first ternary halogen‐rich nonlinear optical chalcohalide Sn7Br10S2 exhibits a strong phase‐matchable second‐harmonic generation response (1.5 × AGS@2.1 μm) and high laser‐induced damage threshold (6.3 × AGS). This work provides a competitive candidate with good performance, facile synthesis and simple chemical composition for infrared nonlinear optical (IR NLO) applications, and also introduces a facile strategy to obtain high‐performance NLO materials via a symmetry break.