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Issue 41, 2012
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Thermally and photo-induced spin crossover behaviour in an Fe(ii) imidazolylimine complex: [FeL3](ClO4)2

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Abstract

Herein we report the synthesis, structure and magnetic properties of [FeL3](ClO4)2, 1, where L is the bidentate ligand N-(4-methoxyphenyl)-1H-imidazol-2-yl-methanimine. Complex 1 crystallises as the mer-isomer which is stabilised by intramolecular π–π interactions between the methoxyphenyl ‘tail’ and imidazole ‘head’ of adjacent ligands centred around Fe(II). The crystal lattice is devoid of any significant intermolecular π–π interactions between neighbouring complexes, although hydrogen bonding between two imidazole N–H groups and two perchlorate anions links two adjacent complexes together and allows them to buttress up against one another. Structural data collected at 116 and 292 K suggest a spin-crossover (SCO) behaviour for 1 as Fe–N bond lengths increase by ca. 10% at the higher temperature. SCO behaviour is confirmed by magnetic susceptibility measurements. The χT vs. T data reveals a complete and reversible SCO for 1 with T1/2 of 158 K, and this is further confirmed by Mössbauer spectroscopy (at 4.2 and 293 K) and variable temperature reflectivity measurements. Indeed, upon irradiation with red light (647 nm) at 10 K, 1 shows a photo-induced spin-crossover and undergoes full switching between the LS and HS states.

Graphical abstract: Thermally and photo-induced spin crossover behaviour in an Fe(ii) imidazolylimine complex: [FeL3](ClO4)2

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Article information


Submitted
03 Aug 2012
Accepted
03 Sep 2012
First published
03 Sep 2012

Dalton Trans., 2012,41, 12720-12725
Article type
Paper

Thermally and photo-induced spin crossover behaviour in an Fe(II) imidazolylimine complex: [FeL3](ClO4)2

J. R. Thompson, R. J. Archer, C. S. Hawes, A. Ferguson, A. Wattiaux, C. Mathonière, R. Clérac and P. E. Kruger, Dalton Trans., 2012, 41, 12720
DOI: 10.1039/C2DT31776A

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