Oxychalcogenides are receiving increasing interest as nonlinear-optical (NLO) materials because of the possible combination of advantages from oxides and chalcogenides. Here, two new pentanary oxythiogermanates Eu2MGe2OS6 [M = Zn (1), Cd (2)] were obtained by the facile metal oxide–boron–sulfur solid-state route. They crystallize with a melilite-type structure and feature {[MGe2OS6]4–}∞ layers built by Ge2OS6 dimers and MS4 tetrahedra. Their optical band gaps are 2.37 and 2.38 eV. As the first NLO rare-earth (RE)/d10 dual-metal oxychalcogenides, they exhibit phase-matchable NLO responses and enhanced laser-induced damage thresholds. Theoretical calculations show that the NLO responses are predominantly contributed by the EuOS7 motifs. This work provides the potential of RE/d10 dual-metal-based NLO materials.

Rare-Earth/d10 Dual-Metal Oxychalcogenides as Infrared Nonlinear-Optical Materials