Halogen Substitution Effects on N2 O Schiff Base Ligands in Unprecedented Abrupt FeII Spin Crossover Complexes.
Chemistry
; 23(29): 7052-7065, 2017 May 23.
Article
em En
| MEDLINE
| ID: mdl-28474778
A family of halogen-substituted Schiff base iron(II) complexes, [FeII (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, 295â
K (X=I) up to 342â
K (X=Br), these being some of the highest T1/2 values obtained, to date, for FeII N/O species. We have recently reported subtle symmetry breaking in [FeII (qsal-Cl)2 ] 2 with two spin transition steps occurring at 308 and 316â
K. A photomagnetic study reveals almost full HS conversion of [FeII (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 [FeII (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, [FeIII (qsal-X)2 ]+ , the two extra π-π and P4AE interactions found in [FeII (qsal-X)2 ] compounds, are believed to be accountable for the spin transitions occurring at ambient temperatures.
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2017
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Article