[Ba4(S2)][ZnGa4S10]: Design of an Unprecedented Infrared Nonlinear Salt‐Inclusion Chalcogenide with Disulfide‐Bonds

Abstract Salt‐inclusion chalcogenides (SICs) have been receiving widespread attention due to their large second harmonic generation (SHG) responses and wide bandgaps, however most of them suffer from small birefringence limiting their technical application. Herein, by introducing the π ‐conjugated (S 2 ) 2− units in the ionic guest of salt‐inclusion structure, the first disulfide‐bond‐containing SIC, [Ba 4 (S 2 )][ZnGa 4 S 10 ] has been synthesized. It exhibits the widest bandgap up to 3.39 eV among polychalcogenides and strong SHG response as large as that of AgGaS 2 (AGS). Importantly, its birefringence reaches a max value of 0.053@1064 nm among AGS‐like SICs, indicating it is a promising IR nonlinear optical (NLO) material. Theoretical calculations reveal that the π ‐conjugated (S 2 ) 2− units and covalent GaS layers favor the enhanced birefringence and large SHG response. This work provides not only a new type of SIC for the first time, but also new lights on the design of IR NLO materials.