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

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 â?? 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 spinstate thermo- and piezoswitching in relation to the structural and elastic properties. Indeed, a pressure-induced spin cross- over (centered at P1/2 â?? 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. © 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.