A review of the structural diversity of [P x S y ] n − motifs and their potential application prospects in metal thiophosphates

Abstract Metal thiophosphates have wide potential critical applications in various fields, such as nonlinear optical materials, magnetic materials, photoluminescence materials and solid electrolytes. However, a detailed review of the relationship among structure, performance and application in thiophosphates has not been reported so far. In this work, we have undertaken integrated generalization for the structural features and application prospects of 312 known metal thiophosphates (117 ternary and 195 quaternary). A survey of their crystal structures shows that they have various link modes used to form the [P x S y ] n − ligands through the [PS 4 ] 3− building unit, for example, the ethane-like [P 2 S 6 ] 4− dimer, edge-sharing [P 2 S 6 ] 2− , corner-sharing [P 2 S 7 ] 4− , cyclic [P 3 S 9 ] 3− cluster, corner-sharing [P 3 S 10 ] 5− cluster, corner-sharing [P 4 S 13 ] 6− cluster and corner-sharing [P 4 S 12 ] 4− ring. Interestingly, various (P-S) ligands can also link other motifs to compose different structural features including zero-dimensional (0D) clusters, 1D chains, 2D layers and 3D networks. A detailed survey provides clear recognition of the inherent structure–performance relationship for thiophosphates and this result also illustrates that thiophosphates have huge potential as superior multifunctional materials.