Thermal trapped iron(II) high spin state investigated by X-ray diffraction

The possibilities to trap by flash cooling the high spin (HS) state of iron(II) in the [Fe(PM–BiA)2(NCS)2] complex have been investigated by X-ray diffraction. This study reveals that trapping the HS state is possible under some conditions depending on the final temperature. If the latter is lower than the T(LIESST) temperature, the HS→LS (low spin) relaxation is slow enough to determine the trapped HS crystal structure by X-ray diffraction. The crystal structure of this complex in the 30 K trapped HS state shows differences from either the room temperature (HS) or the 30 K (LS) crystal structures, as for example differences in the strength of the S⋯H–C hydrogen bond like intermolecular interaction or the π–π interactions, known to play a crucial role in this compound for the propagation of the change in spin at the spin crossover (SCO), i.e. the cooperativity. The differences in intermolecular interactions are directly linked to the differences between the crystallographic unit cell modifications induced by pure thermal effects and those induced by the SCO.