Organic–inorganic interactions revealed by Raman spectroscopy during reversible phase transitions in semiconducting [(C2H5)4N]FeCl4

Abstract

The alkylammonium halogenoferrate families are subjected to diverse studies according to their wide field application. However, these compounds show various transitions depending on the preparation process. In this paper, the [(C₂H₅)₄N]FeCl₄ compound was successfully synthesized using a slow evaporation solution growth method at room temperature. An optical absorption measurement confirms the semiconductor nature with a band gap around 2.95 eV. The X-ray powder diffraction (XRPD) data confirmed the formation of a single-phase with hexagonal-type structure. The differential scanning calorimetry (DSC) indicated that the [(C₂H₅)₄N]FeCl₄ compound undergoes eight reversible phase transitions between 193 and 443 K. At high temperature (T > 423 K) the plastic nature of the crystals was confirmed. Temperature-controlled X-ray diffraction reveals that the thermal expansion of the crystal structure is non homothetic in the (a,b) plane and along the c axis. The temperature dependence of the Raman spectra up to 443 K revealed specific reorientations and molecular displacements of the organic and inorganic components associated with the phase transitions. We aim to thermally stabilize the [(C₂H₅)₄N]FeCl₄ compound which has a band gap suitable for photocatalytic processes.