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Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2016

Magnetic bistability in macrocycle-based FeII spin-crossover complexes : counter ion and solvent effects

Résumé

Two new iron(II) complexes of formula [Fe(L2)](tcm)2·2H2O (1) and [Fe(L2)][Ni(CN)4]·H2O (2) {L2 = 1,8-bis(2′-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane; tcm– = [C(CN)3]– = tricyanomethanide anion} have been synthesized and characterized by X-ray diffraction and magnetic measurements and compared with the previously described compound of the same series [Fe(L2)](BF4)2·H2O (3). The crystal structures of the three compounds show discrete iron(II) complexes in which the FeII ions adopt distorted FeN6 octahedral geometries. A hydrogen-bonding network involving the water molecules and the different counter ions, tcm– in 1 and [Ni(CN)4]2– in 2, leads to chains for both compounds whereas compound 3 reveals no significant intermolecular contacts. For 1, the magnetic measurements show an abrupt and incomplete high-spin→low-spin (HS→LS) spin transition (ST) with a hysteresis of 9 K (T1/2down = 136 K; T1/2up = 145 K) that is also optically observed. Compound 2 presents slightly weaker intermolecular contacts and shows an abrupt ST at 85 K without hysteretic behaviour. Finally, compound 3, in which the FeII complex is well isolated, exhibits a gradual spin transition centred at 150 K. Detailed X-ray diffraction studies performed at various temperatures (293–120 K) show strong modifications of the iron coordination sphere in 1 and 3, in agreement with the presence of a ST in this temperature range in both complexes.

Dates et versions

hal-01432214 , version 1 (11-01-2017)

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Eric Milin, Bouabdellah Benaicha, Fatima El Haji, Véronique Patinec, Smail Triki, et al.. Magnetic bistability in macrocycle-based FeII spin-crossover complexes : counter ion and solvent effects. European Journal of Inorganic Chemistry, 2016, 34, pp.5305-5314. ⟨10.1002/ejic.201600660⟩. ⟨hal-01432214⟩
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