Vibrational study of layered ZnPS3 compounds intercalated with [Co(η5 -C5H5)2+] and [Cr(η6 -C6H6)2+] CATIONS

Infrared and Raman spectra (10–3100 cm^?1) of the layered ZnPSs compound and of intercalates with Co(η⁵ ? C₅H₅)₂⁺] and Cr(η⁶ ? C₆H₆)₂⁺] cations in the polycrystalline state have been recorded 300–10 K temperature range. A complete assignment of the spectra is proposed in terms of PSs group motions, Zn²⁺ ion translations and Co(η⁵ ? C₅H₅)₂⁺] or Cr(η⁶ ? C₆H₆)₂⁺] internal vibrations. New low frequency for the Co(η⁵-C₅H₅)₂⁺] intercalate at low temperature are assigned to librational and torsional modes of C₅H₅ rings. Moreover, the preresonance Raman spectra of this intercalate show a selective enhancement for the metal-ligand vibrations when the charge transfer band of the cobalticenium is approached. One concludes that guest molecules are intercalated under their cationic form, are weakly interacting with the host lattice and seem to be dynamically disordered at room temperature.