Nonlinear Optical Sulfides LiMGa₈ S₁₄ (M = Rb/Ba, Cs/Ba) Created by Li⁺ Driven 2D Centrosymmetric to 3D...

Cations that can regulate the configuration of anion group are greatly important but regularly unheeded. Herein, the structural transformation from 2D CS to 3D noncentrosymmetric (NCS, which is the prerequisite for second-order NLO effect) is rationally designed to newly afford two sulfides LiMGa₈ S₁₄ (M = Rb/Ba, 1; Cs/Ba, 2) by introducing the smallest alkali metal Li⁺ cation into the interlamination of 2D centrosymmetric (CS) RbGaS₂ . The unusual frameworks of 1 and 2 are constructed from C₂ -type [Ga₄ S₁₁ ] supertetrahedrons in a highly parallel arrangement. 1 and 2 display distinguished NLO performances, including strong phase-matchable second-harmonic generation (SHG) intensities (0.8 and 0.9 × AgGaS₂ at 1910 nm), wide optical band gaps (3.24 and 3.32 eV), and low coefficient of thermal expansion for favorable laser-induced damage thresholds (LIDTs, 4.7, and 7.6 × AgGaS₂ at 1064 nm), which fulfill the criteria of superior NLO candidates (SHG intensity >0.5 × AGS and band gap >3.0 eV). Remarkably, 1 and 2 melt congruently at 873.8 and 870.5 °C, respectively, which endows them with the potential of growing bulk crystals by the Bridgeman-Stockbarge method. This investigated system provides a new avenue for the structural evolution from layered CS to 3D NCS of NLO materials.