Experimental and theoretical studies on the NLO properties of two quaternary non-centrosymmetric chalcogenides: BaAg 2 GeS 4 and BaAg 2 SnS 4 .

New middle and far-infrared (MFIR) nonlinear optical (NLO) chalcogenides have been receiving increasing attention for their great importance in military and civil fields. In addition, the current challenge in the efforts for identifying a promising MFIR NLO material lies in achieving simultaneously large second-harmonic generation (SHG) intensity and high laser-induced damage threshold (LIDT) in the same material. In this study, two quaternary non-centrosymmetric (NCS) sulfides, BaAg2 GeS4 (1) and BaAg2 SnS4 (2), were synthesized from a high-temperature solid-state reaction using BaCl2 flux in evacuated closed silica tubes. Although 1 and 2 show identical stoichiometry, they crystallize in different NCS space groups, tetragonal I4[combining macron]2m (no. 121) and orthorhombic I222 (no. 23), respectively, based on the results of crystal structure solution. In their structures, highly distorted AgS4 tetrahedra interconnect together via corner-sharing to form two-dimensional (2D) layers, which are further bridged with isolated GeS4 or SnS4 units to produce a three-dimensional (3D) framework structure with Ba cations lying in the tunnels. Remarkably, they not only possess phase-matchable (PM) abilities but also exhibit a good balance between strong SHG responses (1.7× and 0.4× AgGaS2 ) and high LIDTs (3.2× and 1.5× AgGaS2 ). Moreover, theoretical calculations based on density functional theory (DFT) methods have aided the understanding of energy bands, electronic structures, and linear and NLO properties.