Contribution of Coulomb Interactions to a Two-Step Crystal Structure Phase Transformation Coupled with a Significant Change in Spin Crossover Behavior for a Series of Charged Fe Complexes from 2,6-Bis(2-methylthiazol-4-yl)pyridine.

A series of [Fe(L)](BF) compounds were structurally and physically characterized (L = 2,6-bis(2-methylthiazol-4-yl)pyridine). A crystal structure phase transformation from dihydrate compound 1 to anhydrous compound 3 through partially hydrated compounds 2 and 2' upon dehydration was found. Compounds 1 and 3 exhibited a gradual spin crossover (SCO) conversion, whereas compounds 2 and 2' demonstrated two-step and one-step abrupt SCO transitions, respectively. An X-ray single-crystal structural analysis revealed that one-dimensional and two-dimensional Fe cation networks linked by π stacking and sulfur-sulfur interactions were formed in 1 and 3, respectively. A thermodynamic analysis of the magnetic susceptibility for 1, 2', and 3 suggests that the enthalpy differences may govern SCO transition behaviors in the polymorphic compounds 2' and 3. A structural comparison between 1 and 3 indicates that the SCO behavior variations and crystal structure transformation in the present [Fe(L)](BF) compounds can be interpreted by the relationship between the lattice enthalpies mainly arising from Coulomb interactions between the Fe cations and BF anions as in typical ionic crystals.