Dynamic spin interchange in a tridentate Fe(III) Schiff-base compound

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Abstract

The thermosalient effect is still a rare and poorly understood phenomenon, where crystals suddenly jump, bend, twist or explode upon undergoing a thermally activated phase transition. The synthesis and characterisation of the new spin transition Fe(iii) compound [Fe(5-Br-salEen)2][ClO4] (salEen = N-ethyl-N-(2-aminoethyl)salicylaldiminate) is described and its thermosalient behaviour reported. It is the first example of a thermosalient effect with a spin transition and magnetic, calorimetric, diffraction, microscopy and computational studies are used to characterise these effects. Both thermosalient effect and spin transition occur around 320 K upon heating and are accompanied by an anisotropic unit cell change with conservation of crystal symmetry that causes a large enough stress of the crystal lattice to induce crystal explosion. This stress can ultimately be traced back to a diffusionless and distortive structural perturbation resulting in a coupled spin transition-thermosalient effect.

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Vicente, A. I., Joseph, A., Ferreira, L. P., De Deus Carvalho, M., Rodrigues, V. H. N., Duttine, M., … Martinho, P. N. (2016). Dynamic spin interchange in a tridentate Fe(III) Schiff-base compound. Chemical Science, 7(7), 4251–4258. https://doi.org/10.1039/c5sc04577k

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