Spin-Crossover Behaviors of Iron(II) Complexes Bearing Halogen Ligands in Solid State and Solution

Numerous Fe(II) spin-crossover (SCO) compounds have been developed in the past decades, while the reports on the SCO materials with halogen atoms acting as coordinating ligands remain rare. In this study, we synthesize three iron(II) halide complexes with a general formula of [Fe^II(Py5Me₂)X]⁺ (Py5Me₂ = 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine, X = Cl^- or Br^-) that undergo complete SCO transitions at near room temperature. The SCO properties of these compounds are investigated in detail by magnetic measurements, variable-temperature single-crystal X-ray diffractions, and Mössbauer spectra analyses. Because of the good stability of the coordination structures and suitable ligand-field strength, these compounds show robust spin transitions in both solid state and solution.