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Gaspar A.B.,University of Valencia | Levchenko G.,Donetsk Physical and Technical Institute NAS of Ukraine | Terekhov S.,Donetsk Physical and Technical Institute NAS of Ukraine | Bukin G.,Donetsk Physical and Technical Institute NAS of Ukraine | And 5 more authors.
European Journal of Inorganic Chemistry | Year: 2014

The effect of pressure on the spin-transition properties of the 2D coordination polymer {Fe(phpy)2[Ni(CN)4]} is reported. The study has been carried out by means of variable-temperature (10-310 K) magnetic susceptibility measurements at applied pressures of 105 Pa to 1.0 GPa and spectroscopic studies in the visible region at room temperature (10 5 Pa-3.0 GPa). As the pressure is increased, the characteristic temperature of the spin transition is displaced to higher temperatures and the thermal hysteresis loop disappears. A cooperative first-order spin transition characterized by a piezo-hysteresis loop about 0.3 GPa wide was observed at 293 K. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Martinez V.,University of Valencia | Martinez V.,Monash University | Castillo Z.A.,University of Valencia | Munoz M.C.,Polytechnic University of Valencia | And 7 more authors.
European Journal of Inorganic Chemistry | Year: 2013

The thermal spin-crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure-induced spincrossover behaviour at 298 K are discussed for the non-porous two-dimensional Hofmann-like coordination polymer [Fe(3-Clpy)2Pd(CN)4] (1). The title compound undergoes a two-step, cooperative thermal-induced SCO with critical temperatures Tc1 ↓ = 159.6 K and Tc1 ↑ = 164.5 K for the first step and Tc2 ↓ = 141.4 K and Tc2 ↑ = 148.4 K for the second step. Irradiation of the low-spin state with green light (514 nm) at 10 K induced the photoexcitation of around 60% of the iron(II) centres to the high-spin state (LIESST effect). The subsequent cooperative relaxation processes were recorded at several temperatures and analysed. The effect of cooperativity on the photoexcitation was investigated by the LITH (light-induced thermal hysteresis) procedure. At 300 K, the coordination polymer 1 underwent a cooperative spincrossover transition at around 0.6 GPa. The thermodynamic analysis of the pressure-induced SCO transition afforded the enthalpy and cooperativity parameters ΔHHL(p) = 22.01 kJmol-1 and λ(p) = 7.47 kJmol-1, consistent with previous results. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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