Phase transition sequences in tetramethylammonium tetrachlorometallates by X-ray diffraction and spectroscopic measurements
The phase transition sequences of two members of the tetramethylammonium tetrachlorometallate(III) family of hybrid organic–inorganic salts have been determined and structurally characterized as a function of temperature for the first time. Unusually, a reduction in point-group symmetry with increasing temperature until reaching a cubic prototype phase is observed. Two additional intermediate phases are observed for Fe3+. First-principles calculations and the presence of short Cl...Cl contacts for Ga3+suggest the [GaCl4]−anion to be conformationally hindered due to stronger lone-pair–σ-hole interactions. The conformationally more flexible Fe3+structures show sublattice melting with the onset of rotational disorder in the [NMe4]+cations occurring 40 K below the corresponding onset of rotational disorder in the [FeCl4]−sublattice.