TISSOT, Antoine; SHEPHERD, Helena; TOUPET, Loic; COLLET, Eric; SAINTON, Joëlle; MOLNÁR, Gábor; GUIONNEAU, Philippe; BOILLOT, Marie-Laure

doi:10.1002/ejic.201201059

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TISSOT, Antoine
Institut de Chimie Moléculaire et des Matériaux d'Orsay [ICMMO]

SHEPHERD, Helena
Department of Chemistry
Laboratoire de chimie de coordination [LCC]

TOUPET, Loic
Institut de Physique de Rennes [IPR]

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European Journal of Inorganic Chemistry. 2013, vol. 2013, n° 5-6, p. 1001-1008

Wiley-VCH Verlag

Résumé en anglais

The [(TPA)FeIII(TCC)]+ complex [TPA = tris(2-pyridylmethyl)amine, TCC2- = 3,4,5,6-tetrachlorocatecholate dianion] forms a molecular solid with the SbF6- anion, which exhibits an incomplete S = 1/2 ↔ S = 5/2 thermal spin-crossover process centered at 250 K. Single-crystal X-ray diffraction, Raman spectroscopy, and magnetic measurements of this orthorhombic polymorph were performed to delineate the spin-state thermo- and piezoswitching in relation to the structural and elastic properties. Indeed, a pressure-induced spin crossover (centered at P1/2 ≈ 1.65 kbar, T = 294 K) concomitant with unit-cell contraction was observed by applying a hydrostatic pressure to the single crystal. Under ambient conditions, the piezo-induced transition, like that induced thermally, is relatively gradual, which probably reflects a similar mechanism in response to both stimuli. Except for a 47 K shift, the spin-crossover curves of the isostructural SbF6- and PF6- salts compare well. They are discussed with respect to structural anisotropy and pressure effects.< Réduire

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Iron

Spin crossover

Raman spectroscopy

X-ray diffraction

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Temperature- and pressure-induced switching of the molecular spin state of an orthorhombic iron(II) spin-crossover salt

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