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 [PS₄]³⁻ building unit, for example, the ethane-like [P₂S₆]⁴⁻ dimer, edge-sharing [P₂S₆]²⁻, corner-sharing [P₂S₇]⁴⁻, cyclic [P₃S₉]³⁻ cluster, corner-sharing [P₃S₁₀]⁵⁻ cluster, corner-sharing [P₄S₁₃]⁶⁻ cluster and corner-sharing [P₄S₁₂]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.

金属硫代磷酸盐在非线性光学材料、磁性材料、光致发光材料和固体电解质等各个领域具有广泛的潜在关键应用。然而，迄今为止尚未报道过关于硫代磷酸盐的结构、性能和应用之间关系的详细综述。在这项工作中，我们对 312 种已知金属硫代磷酸盐（117 三元和 195 四元）的结构特征和应用前景进行了综合概括。对其晶体结构的调查表明，它们具有用于通过 [PS ₄ ] ^3-构建单元形成 [P _x S _y ] ^{n -}配体的各种连接模式，例如类乙烷 [P ₂ S ₆ ] ⁴⁻二聚体，边缘共享 [P ₂ S ₆ ] ²⁻，角共享 [P ₂ S ₇ ] ⁴⁻，循环 [P ₃ S ₉ ] ³⁻簇，角共享 [P ₃ S ₁₀ ] ⁵⁻簇，角点共享 [P ₄ S ₁₃ ] ⁶⁻簇和角点共享 [P ₄ S ₁₂ ] ⁴⁻戒指。有趣的是，各种 (PS) 配体还可以连接其他基序以组成不同的结构特征，包括零维 (0D) 簇、1D 链、2D 层和 3D 网络。详细的调查清楚地认识到硫代磷酸盐的内在结构-性能关系，这一结果也说明硫代磷酸盐作为优异的多功能材料具有巨大的潜力。