Thermal-, Pressure- and Light-Induced Spin-Crossover Behaviour in the Two-Dimensional Hofmann-Like Coordination Polymer [Fe(3-Clpy)2Pd(CN)4]

The thermal spin‐crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure‐induced spin‐crossover 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, coo...

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Published in:	European journal of inorganic chemistry Vol. 2013; no. 5-6; pp. 813 - 818
Main Authors:	Martínez, Víctor, Arcís Castillo, Zulema, Muñoz, M. Carmen, Gaspar, Ana B., Etrillard, C., Létard, Jean-François, Terekhov, Sergey A., Bukin, Gennadiy V., Levchenko, Georgiy, Real, José A.
Format:	Journal Article
Language:	English
Published:	Weinheim WILEY-VCH Verlag 01-02-2013 WILEY‐VCH Verlag Wiley Subscription Services, Inc
Subjects:	Absorption Coordination polymers Critical temperature Enthalpy Hysteresis Iron Irradiation Photoexcitation Photomagnetism Spin crossover Thermodynamics Two dimensional
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Abstract	The thermal spin‐crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure‐induced spin‐crossover 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 spin‐crossover 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 kJ mol–1 and Γ(p) = 7.47 kJ mol–1, consistent with previous results. The thermal spin‐crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure‐induced spin‐crossover behaviour at 300 K are discussed for the non‐porous two‐dimensional Hofmann‐like coordination polymer [Fe(3‐Clpy)2Pd(CN)4].
AbstractList	The thermal spin-crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure-induced spin-crossover 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[left right arrow with stroke] = 159.6 K and Tc1[arrow up] = 164.5 K for the first step and Tc2[left right arrow with stroke] = 141.4 K and Tc2[arrow up] = 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 spin-crossover transition at around 0.6 GPa. The thermodynamic analysis of the pressure-induced SCO transition afforded the enthalpy and cooperativity parameters [Delta]HHL(p) = 22.01 kJmol-1 and [Gamma](p) = 7.47 kJmol-1, consistent with previous results. [PUBLICATION ABSTRACT] The thermal spin‐crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure‐induced spin‐crossover behaviour at 298 K are discussed for the non‐porous two‐dimensional Hofmann‐like coordination polymer [Fe(3‐Clpy) 2 Pd(CN) 4 ] ( 1 ). The title compound undergoes a two‐step, cooperative thermal‐induced SCO with critical temperatures T c1 ↓ = 159.6 K and T c1 ↑ = 164.5 K for the first step and T c2 ↓ = 141.4 K and T c2 ↑ = 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 spin‐crossover transition at around 0.6 GPa. The thermodynamic analysis of the pressure‐induced SCO transition afforded the enthalpy and cooperativity parameters Δ H HL ( p ) = 22.01 kJ mol –1 and Γ ( p ) = 7.47 kJ mol –1 , consistent with previous results. The thermal spin-crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure-induced spin-crossover behaviour at 298 K are discussed for the non-porous two-dimensional Hofmann-like coordination polymer [Fe(3-Clpy) sub(2)Pd(CN) sub(4)] (1). The title compound undergoes a two-step, cooperative thermal-induced SCO with critical temperatures T sub(c1) super([downwardsarrow]) = 159.6 K and T sub(c1) super([uarr) = 164.5 K for the first step and T sub(c2) super([downwardsarrow]) = 141.4 K and T sub(c2) super([uarr) = 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 spin-crossover transition at around 0.6 GPa. The thermodynamic analysis of the pressure-induced SCO transition afforded the enthalpy and cooperativity parameters Delta H sub(HL)(p) = 22.01 kJmol super(-1) and Gamma (p) = 7.47 kJmol super(-1), consistent with previous results. The thermal spin-crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure-induced spin-crossover behaviour at 300 K are discussed for the non-porous two-dimensional Hofmann-like coordination polymer [Fe(3-Clpy) sub(2)Pd(CN) sub(4)]. The thermal spin‐crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure‐induced spin‐crossover 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 spin‐crossover 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 kJ mol–1 and Γ(p) = 7.47 kJ mol–1, consistent with previous results. The thermal spin‐crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure‐induced spin‐crossover behaviour at 300 K are discussed for the non‐porous two‐dimensional Hofmann‐like coordination polymer [Fe(3‐Clpy)2Pd(CN)4].
Author	Real, José A. Muñoz, M. Carmen Etrillard, C. Levchenko, Georgiy Arcís Castillo, Zulema Gaspar, Ana B. Martínez, Víctor Létard, Jean-François Terekhov, Sergey A. Bukin, Gennadiy V.
Author_xml	– sequence: 1 givenname: Víctor surname: Martínez fullname: Martínez, Víctor organization: Institut de Ciencia Molecular (ICMol), Universitat de València, c/ Catedrático, José Beltrán Martínez 2, 46980 Paterna (València), Spain, http://www.uv.es – sequence: 2 givenname: Zulema surname: Arcís Castillo fullname: Arcís Castillo, Zulema organization: Institut de Ciencia Molecular (ICMol), Universitat de València, c/ Catedrático, José Beltrán Martínez 2, 46980 Paterna (València), Spain, http://www.uv.es – sequence: 3 givenname: M. Carmen surname: Muñoz fullname: Muñoz, M. Carmen organization: Departamento de Física Aplicada, Universitat Politècnica de València, Camino de Vera s/n, 46022 València, Spain – sequence: 4 givenname: Ana B. surname: Gaspar fullname: Gaspar, Ana B. organization: Institut de Ciencia Molecular (ICMol), Universitat de València, c/ Catedrático, José Beltrán Martínez 2, 46980 Paterna (València), Spain, http://www.uv.es – sequence: 5 givenname: C. surname: Etrillard fullname: Etrillard, C. organization: CNRS, ICMCB, UPR 9048, 33600 Pessac, France – sequence: 6 givenname: Jean-François surname: Létard fullname: Létard, Jean-François organization: CNRS, ICMCB, UPR 9048, 33600 Pessac, France – sequence: 7 givenname: Sergey A. surname: Terekhov fullname: Terekhov, Sergey A. organization: Donetsk Physical & Technical Institute NAS of Ukraine, Donetsk, Ukraine – sequence: 8 givenname: Gennadiy V. surname: Bukin fullname: Bukin, Gennadiy V. organization: Donetsk Physical & Technical Institute NAS of Ukraine, Donetsk, Ukraine – sequence: 9 givenname: Georgiy surname: Levchenko fullname: Levchenko, Georgiy organization: Donetsk Physical & Technical Institute NAS of Ukraine, Donetsk, Ukraine – sequence: 10 givenname: José A. surname: Real fullname: Real, José A. email: jose.a.real@uv.es organization: Institut de Ciencia Molecular (ICMol), Universitat de València, c/ Catedrático, José Beltrán Martínez 2, 46980 Paterna (València), Spain, http://www.uv.es
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Snippet	The thermal spin‐crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure‐induced spin‐crossover behaviour at 298 K are... The thermal spin-crossover behaviour, photoexcitation and subsequent relaxation, as well as the pressure-induced spin-crossover behaviour at 298 K are...
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SubjectTerms	Absorption Coordination polymers Critical temperature Enthalpy Hysteresis Iron Irradiation Photoexcitation Photomagnetism Spin crossover Thermodynamics Two dimensional
Title	Thermal-, Pressure- and Light-Induced Spin-Crossover Behaviour in the Two-Dimensional Hofmann-Like Coordination Polymer [Fe(3-Clpy)2Pd(CN)4]
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