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Pressure-induced switching properties of the iron(iii) spin-transition complex [FeIII(3-OMeSalEen)2]PF6

Laisney, J., Shepherd, H.J., Rechignat, L., Molnár, G., Rivière, E., Boillot, M.-L. (2018) Pressure-induced switching properties of the iron(iii) spin-transition complex [FeIII(3-OMeSalEen)2]PF6. Physical Chemistry Chemical Physics, 20 . pp. 15951-15959. ISSN 1463-9076. (doi:10.1039/C8CP02376J) (KAR id:67342)

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We investigated the effect of an externally applied pressure on the iron(III) Schiff-base compound [Fe(3-OMeSalEen)2]PF6 (H-3-OMeSalEen, condensation product of 3-methoxy-substituted salicylaldehyde and N-ethylethylenediamine), which at ambient pressure displays a thermal spin transition with a 3 K wide hysteresis loop centered at 164 K. Raman spectrometry revealed the occurrence of a complete spin-state switching process for a pressure of P1/2 = 8–9 kbar at room temperature. The evolution of lattice parameters as a function of pressure was followed by X-ray diffraction measurements on single crystals, highlighting the important microscopic aspects at the origin of the pressure-induced transition, i.e. an anisotropic response and a high compressibility of the HS molecular lattice. Variable temperature magnetic susceptibility measurements at different applied pressures revealed the smoothening of the spin transition curves and a linear increase of the transition temperatures by ca. 16.4 (1.0) K kbar?1, in good agreement with the Clausius–Clapeyron law. The non-negligible influence of the pressure transmitting oils on the intrinsic transition properties was also evidenced and attributed to mechanical interactions between the particles and the solidified matrix.

Item Type: Article
DOI/Identification number: 10.1039/C8CP02376J
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > School of Physical Sciences
Depositing User: Helena Shepherd
Date Deposited: 15 Jun 2018 14:44 UTC
Last Modified: 16 Feb 2021 13:55 UTC
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