Oxychalcogenides as Promising Ultraviolet Nonlinear Optical Candidates: Experimental and Theoretical Studies of AEGeOS 2 (AE = Sr and Ba).

Oxychalcogenides have gained widespread attention as promising infrared nonlinear optical (IR-NLO) candidates. However, high-performance oxychalcogenides have rarely been reported in the ultraviolet (UV) region owing to the low energy gaps ( E g < 4.0 eV). Herein, two non-centrosymmetric (NCS) oxychalcogenides with one-dimensional (1D) chain structures and wide E g (>4.3 eV), namely, AEGeOS 2 (AE = Sr and Ba), have been discovered by combined experiments and theory calculations as a new source of UV-NLO materials. Significantly, they exhibit excellent comprehensive performance comparable to the commercial UV-NLO material KH 2 PO 4 (KDP), including large phase-matching ranges (>380 nm), sufficient second harmonic generation intensities (0.7-1.1 × KDP), high laser-induced damage thresholds (1.2 × KDP), wide transparent regions (0.26-12.2 μm), and good thermal stability (up to 1100 K). Moreover, systematic structure-activity relationship analysis illustrates that the 1D homochiral helical [GeOS 2 ] 2- chains composed of heteroanionic [GeS 2 O 2 ] units make major contribution to the desirable UV-NLO performance. This work makes the two compounds shine out as new energy in the UV-NLO field and offers a new perspective for the exploration of structure-driven functional oxychalcogenides.