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

Chem Sci. 2016 Jul 1;7(7):4251-4258. doi: 10.1039/c5sc04577k. Epub 2016 Mar 17.

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.