PHONSRI, Wasinee; MACEDO, David S.; VIGNESH, Kuduva R.; RAJARAMAN, Gopalan; DAVIES, Casey G.; JAMESON, Guy N. L.; MOUBARAKI, Boujemaa; WARD, Jas S.; KRUGER, Paul E.; CHASTANET, Guillaume; MURRAY, Keith S.

doi:10.1002/chem.201700232

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PHONSRI, Wasinee
School of Chemistry

MACEDO, David S.
School of Chemistry

VIGNESH, Kuduva R.
IITB-Monasch Research Academy

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Chemistry - A European Journal. 2017-05-23, vol. 23, n° 29, p. 7052-7065

Wiley-VCH Verlag

Résumé en anglais

A family of halogen-substituted Schiff base iron(II) complexes, [Fe(II) (qsal-X)2 ], (qsal-X=5-X-N-(8-quinolyl)salicylaldimines)) in which X=F (1), Cl (2), Br (3) or I (4) has been investigated in detail. Compound 1 shows a temperature invariant high spin state, whereas the others all show abrupt spin transitions, at or above room temperature, namely, 295 K (X=I) up to 342 K (X=Br), these being some of the highest T1/2 values obtained, to date, for Fe(II) N/O species. We have recently reported subtle symmetry breaking in [Fe(II) (qsal-Cl)2 ] 2 with two spin transition steps occurring at 308 and 316 K. A photomagnetic study reveals almost full HS conversion of [Fe(II) (qsal-I)2 ] 4 at low temperature (T(LIESST)=54 °K). The halogen substitution effects on the magnetic properties, as well as the crystal packing of the [Fe(II) (qsal-X)2 ] compounds and theoretical calculations, are discussed in depth, giving important knowledge for the design of new spin crossover materials. In comparison to the well known iron(III) analogues, [Fe(III) (qsal-X)2 ](+) , the two extra π-π and P4AE interactions found in [Fe(II) (qsal-X)2 ] compounds, are believed to be accountable for the spin transitions occurring at ambient temperatures.< Réduire

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Schiff base ligands

halogen bonding

intermolecular interactions

iron complexes

spin crossover

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Halogen substitution effects on N2O schiff base ligands in unprecedented abrupt Fe(II) spin crossover complexes

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