6533b86dfe1ef96bd12c9fd5

RESEARCH PRODUCT

Pressure-induced cooperative spin transition in ironII 2D coordination polymers: room-temperature visible spectroscopic study.

José Antonio RealVíctor MartínezGeorgiy LevchenkoG. V. BukinMari Carmen MunozAna B. GasparS. A. Terekhov

subject

chemistry.chemical_classificationSpin statesCondensed matter physicsEnthalpySpin transitionElastic energyPolymerSurfaces Coatings and FilmschemistryMean field theorySpin crossoverMaterials ChemistryPhysical chemistryPhysical and Theoretical ChemistrySpin-½

description

For the 2D coordination polymers [Fe(3-Fpy)(2)M(II)(CN)(4)] (M(II) = Ni, Pd, Pt), the pressure-induced spin crossover behavior has been investigated at 298 K by monitoring the distinct optical properties associated with each spin state. Cooperative first-order spin transition characterized by a piezohysteresis loop ca. 0.1 GPa wide was observed for the three derivatives. Application of the mean field regular solution theory has enabled estimation of the cooperative parameter, Γ(p), and the enthalpy, ΔH(HL)(p), associated with the spin transition for each derivative. These values, found in the intervals 6.8-7.9 and 18.6-20.8 kJ mol(-1), respectively, are consistent with those previously reported for thermally induced spin transition at constant pressure for the title compounds (Chem.-Eur. J.2009, 15, 10960). Relevance of the elastic energy, Δ(elast), as a corrective parameter accounting for the pressure dependence of the critical temperature of thermally induced spin transitions (Clausius-Clapeiron equation) is also demonstrated and discussed.

10.1021/jp201585xhttps://pubmed.ncbi.nlm.nih.gov/21599006