Phase Transition and Second Harmonic Generation in Thiophosphates Ag2Cd(P2S6) and AgCd3(PS4)S2 Containing Two Second-Order Jahn–Teller Distorted Cations

Two new phases in the Ag–Cd–P–S system containing two second-order Jahn–Teller (SOJT) distorted d10 cations (Cd2+ and Ag+), namely, Ag2Cd­(P2S6) (1) and AgCd3(PS4)­S2 (2), are obtained via medium-temperature solid-state synthesis. Compound 1 exhibits a two-dimensional layered structure and undergoes a first-order structural phase transition at approximately 280 °C. This outcome can be ascribed to the significant mismatch in the expansion coefficients between Cd–S (Ag–S) and P–P (P–S) bonds evaluated through bond valence theory. The three-dimensional non-centrosymmetric (NCS) framework of 2 is constructed by two types of tetrahedral layers consisting of corner-shared CdS4, AgS4, and PS4 tetrahedra. Compound 2 exhibits second harmonic generation (SHG) intensity of 0.45 times that of commercial AgGaS2 (AGS) at a laser irradiation of 1.85 μm and an optical band gap of 2.56 eV, and no intrinsic vibrational absorption of chemical bonds is observed in the range of 2.5–18.2 μm. Both phase transition in 1 and SHG properties in 2 are closely related to the SOJT distorted d10 cations and diverse phosphorus–sulfur polyanions (PaSb)n−, which together can easily result in NCS distorted structures and interesting properties.