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Thermally and photo-induced spin crossover behaviour in an Fe(ii) imidazolylimine complex: [FeL(3)](ClO(4))(2).
MedLine Citation:
PMID:  22968765     Owner:  NLM     Status:  Publisher    
Abstract/OtherAbstract:
Herein we report the synthesis, structure and magnetic properties of [FeL(3)](ClO(4))(2), , where L is the bidentate ligand N-(4-methoxyphenyl)-1H-imidazol-2-yl-methanimine. Complex 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 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 with T(1/2) 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, shows a photo-induced spin-crossover and undergoes full switching between the LS and HS states.
Authors:
John R Thompson; Rosanna J Archer; Chris S Hawes; Alan Ferguson; Alain Wattiaux; Corine Mathonière; Rodolphe Clérac; Paul E Kruger
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-9-11
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  -     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2012 Sep 
Date Detail:
Created Date:  2012-9-12     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
Affiliation:
Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8041, New Zealand. paul.kruger@canterbury.ac.nz.
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