Temperature- and pressure-induced switching of the molecular spin state of an orthorhombic iron(II) spin-crossover salt
Language
en
Article de revue
This item was published in
European Journal of Inorganic Chemistry. 2013, vol. 2013, n° 5-6, p. 1001-1008
Wiley-VCH Verlag
English Abstract
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 ...Read more >
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.Read less <
English Keywords
Iron
Spin crossover
Raman spectroscopy
X-ray diffraction
Origin
Hal imported