The [Fe(II)L(CN)(2)].H(2)O complex, dicyano[2,13-dimethyl-6,9-dioxa-3,12,18-triazabicyclo[12.3.1]octadeca-1(18),2,12,14,16-pentaene]iron(II) monohydrate, exhibits a thermal induced metal-ligand bond break reversible in the solid state and associated to a spin crossover that corresponds to an unprecedented structurally characterized modification of the coordination metal environment from a hepta-coordinate high spin state to a hexa-coordinate low spin state.
The pressure dependences of the lattice parameters of two spin transition compounds have been derived from neutron powder diffraction measurements at ambient temperature. The study of Fe(PM–AzA)2(NCS)2[PM isN-2′-pyridylmethylene and AzA is 4-(phenylazo)aniline] has been used to validate this new type of investigation of spin crossover compounds, and the study of Fe(PM–BiA)2(NCS)2(BiA is 4-aminobiphenyl) has allowed the atypical spin crossover behaviour of this compound under pressure to be explained. In addition, this complex exhibits a pressure-induced structural transition with an associated symmetry change, inducing the transformation of Fe(PM–BiA)2(NCS)2into a different polymorph that avoids a first-order spin transition in favour of continuous transition.
et al.. X-ray diffraction investigation of a spin crossover hysteresis loop.The nature and the mechanism of the magnetic hysteresis for the thermal spin crossover exhibited by an iron(II) compound is investigated by mean of variable temperature powder and single crystals X-ray diffraction. The unit cell temperature dependence clearly evidences the amplitude of the strong structural re-arrangement that accompanied the spin crossover -corresponding to a variation of 8.6 % for a unit cell parameter -as well as the structural hysteresis width. To this regard, the present X-ray study reveals significant differences in the spin crossover features according to the nature of the sample -powder or single crystal -that should be taken into account in the physical properties analysis. Concerning the interplay between structural and magnetic transitions, quenching effects show that the structural transition and the spin crossover are indissociable. Furthermore, investigations of the mechanism itself of the thermal spin crossover confirm the presence of spin-like domains in the conversion region, either in the cooling or in the warming loops. The non-dependence with temperature of these domains inside the hysteresis loop demonstrates the stability of the microscopic and macroscopic structures in the corresponding thermodynamic conditions. This result is of interest in the context of the potential use of hysteresis loops to obtain high temperature photo-conversion.
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