Cs4Zn5P6S18I2: the Largest Birefringence in Chalcohalide Achieved by Highly Polarizable Nonlinear Optical Functional Motifs

Abstract Chalcohalides not only keep the balance between the nonlinear optical (NLO) coefficient and wide band gap, but also provide a promising solution to achieve sufficient birefringence for phase‐matching ability in NLO crystals. In this study, a novel chalcohalide, Cs 4 Zn 5 P 6 S 18 I 2 ( 1 ) is successfully synthesized, by incorporating the highly electropositive Cs and the large electronegative I element into the zinc thiophosphate. Its 3D open framework features an edge‐shared by distorted [ZnS 4 ], ethanol‐like [P 2 S 6 ], and unusual [ZnS 2 I 2 ] polyhedrons, which is inconsistent with the soft‐hard‐acids‐bases theory. Remarkably, compound 1 simultaneously exhibits the large second‐harmonic generation (SHG, 1.1×AgGaS 2 , @1.3 µm) and a wide band gap (3.75 eV) toward a high laser‐induced damage threshold (16.7×AgGaS 2 , @1.06 µm), satisfying the rigorous requirements for a prominent infrared NLO material with concurrent SHG intensity (≥0.5×AGS) and band gap (≥3.5 eV). Moreover, to the best of the knowledge, the experimental result shows that phase 1 has the largest birefringence (0.108, @546 nm) in chalcohalide and meets phase‐matching behavior demand originating from the polarizable anisotropy of NLO‐functional motifs. This finding may provide great opportunities for designing birefringent chalcohalides.