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

Chemical Science
Ana I VicentePaulo N Martinho

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.

References

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Citations

Jun 25, 2019·Angewandte Chemie·Theerapoom BoonprabDavid J Harding
Jul 16, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Sharon E LazaroDavid J Harding
Jan 18, 2020·IUCrJ·Khushboo YadavaJagadese J Vittal
Oct 7, 2016·Chemical Communications : Chem Comm·Patrick ComminsPanče Naumov
May 9, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Ana I VicentePaulo N Martinho
Aug 23, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Theerapoom BoonprabDavid J Harding
Jan 3, 2021·Environmental Science and Pollution Research International·Rewati DixitPiet Lens
Dec 11, 2019·The Journal of Physical Chemistry. a·Israel Tilahun DestaPanče Naumov
Nov 7, 2019·Journal of the American Chemical Society·Izar Capel BerdiellMalcolm A Halcrow
Oct 9, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Zong-Mei YuShi Wang

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Methods Mentioned

BETA
differential scanning calorimetry
X-ray
single crystal diffraction

Software Mentioned

SADABS
SHELX
PLATON
NT
SAINT
Plus Controler
GAUSSIAN09
Gaussian

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