A series of oxysulfides RE2M2S3O4 (RE = Y, Tm; M = Zr, Hf) featuring a unique MS3O4 motif and {[M2S3O4]8−}∞ wrinkle layer

Abstract

Inorganic salts with multiple anions have recently received increasing interest in view of their structural diversity and multifunctional properties, and oxysulfides are one type of such salts. Here, three novel oxysulfides Y₂Zr₂S₃O₄ (1), Y₂Hf₂S₃O₄ (2), and Tm₂Z₂S₃O₄ (3) are obtained by high-temperature solid-state reactions. They crystallize with the orthorhombic space group Pbam and their three-dimensional structures featuring MS₃O₄ (M = Zr, Hf) motifs built an unprecedented {[M₂S₃O₄]⁸⁻}_∞ wrinkle layer. Their optical band gaps are determined and 3 shows antiferromagnetic-like behavior. Theoretical calculations suggest their direct band gaps and the electron transfer between the frontier orbitals mainly occurred from S-3p and O-2p, to Y-4d and Zr-4d/Hf-5d orbitals.