ESR studies of metallocene intercalated Cd₂P₂S₆

Cd₂P₂S₆ exhibits a layered crystal structure that may be intercalated with metallocenes. The ESR spectra of Cd₂P₂S₆ single crystals intercalated with cobaltocene, nickelocene and chromocene have been examined over the temperature range 280-4.2 K. The spectra indicate that both oxidized and unoxidized metallocene is present in the van der Waals gap of the layered host lattice. Examination of the angle dependence of the ESR spectra establishes the orientation of neutral cobaltocene and nickelocenium cation with the C₅ molecular symmetry axis parallel to the C* axis of the host lattice. The orientation of chromocenium cation is rotated 90° to place C₅ perpendicular to C*.