Relationship between structure parameters and chemical properties in some MPS3 layered phases

Cationic thermal motions in the MPS₃ have been related to substitution abilities in this layer family. They have also been correlated to the crystal field stabilization energy. These considerations explain why some MPS₃ materials may or may not undergo a low temperature substitution intercalation reaction. From interatomic distances comparisons, the bond between (PS₃) groups in the anionic (P₂S₆)^4? octahedra, is found to be easily stretched upon cation substitution. Cationic radii follows the expected variation according to their high spin configuration in octahedral sulfur environment.