Two Mixed-Anion Units of [GeOSe3] and [GeO3S] Originating from Partial Isovalent Anion Substitution and Inducing Moderate Second Harmonic Generation Response and Large Birefringence

Highly polarizable mixed-anion structural building units (SBUs) have been demonstrated as promising candidates for high-performing optical crystals. In this work, two new mixed-anion SBUs of [GeOSe3] and [GeO3S] are first designed through partial isovalent substitution of chalcogen atoms by O atoms in the classical [GeQ(4)] (Q = S, Se) tetrahedra. On the basis of these SBUs, two new quaternary oxychalcogenides, Sr3Ge2O4Se3 and SrGe2O3S2, are successfully synthesized. Sr3Ge2O4Se3 crystallizes in the noncentrosymmetric space group R3m and possesses unique zero-dimensional [Ge2O4Se3](6-) units consisting of highly distorted [GeOSe3] tetrahedra and [GeO4] tetrahedra through a shared O atom. It displays intriguing potential as an infrared nonlinear optical material with a wide band gap (2.96 eV) and moderate second harmonic generation intensity (0.8 X AgGaS2). SrGe2O3S2 belongs to the centrosymmetric space group P2(1)/c and features 2 infinity[Ge2O3S2](2-) layers formed by the corner-shared [GeO3S] tetrahedra. Moreover, the large birefringence of SrGe2O3S2 (calculated Delta n = 0.22-0.17 from 0.4 to 4.0 mu m) gives it a potential as a birefringent material. Theoretical calculations revealed the crucial effects of mixed-anion [GeOSe3] and [GeO3S] units on the moderate second harmonic generation response and large birefringence. The discovery of new mixed-anion SBUs of [GeOSe3] and [GeO3S] will guide the exploration of new functional oxychalcogenides.