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Comptes Rendus Chimie
Volume 15, n° 10
pages 937-942 (octobre 2012)
Doi : 10.1016/j.crci.2012.06.013
Received : 12 April 2012 ;  accepted : 28 June 2012
Chiral single-molecule magnet with a 35K energy barrier for relaxation of the magnetization
 

Ghenadie Novitchi a, , b , Guillaume Pilet a, Dominique Luneau a
a Université Claude-Bernard Lyon-1, laboratoire des multimatériaux et interfaces, UMR 5615, campus de la Doua, 69622 Villeurbanne, France 
b Laboratoire national des champs magnétiques intenses, CNRS UPR 3228, 25, rue des Martyrs, 38042 Grenoble, France 

Corresponding author.
Graphical abstract

Graphical synopsis.

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Abstract

The reaction of [MnII(S -mandelato)2 ] complexes with 5-Methyl-salicylaldoxim (5-Me-saloxH 2 ) leads to the chiral hexanuclear manganese(III) complex [Mn63 -O)2 (5-Me-salox)6 (S -mandelato)2 (EtOH)6 ]. The structure can be viewed as two neutral stacked {Mn33 -O)(5-Me-salox)3 (S -mandelato)(EtOH)3 } triangular subunits linked together in a head-to-tail manner by two phenoxo and two oximato μ3 -oxygen atoms of the deprotonated oxime groups of the ligands. The magnetic study of this chiral hexanuclear manganese(III) complex reveals a SMM behaviour with an energy barrier of the slow relaxation of the magnetisation equal to 35K. Considering the structural features, the fitting of the temperature dependence of the magnetic susceptibility gives a good agreement with the experimental data considering two sets of interactions: J 1 =+0.37cm−1 and J 2 =−0.70cm−1 within (ferromagnetic) and between (antiferromagnetic), respectively, the {Mn33 -O)(5-Me-salox)3 (S -mandelato)(EtOH)3 } triangular subunits.

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Résumé

La réaction du complexe [MnII(S-mandélato)2 ] avec le 5-méthyl-salicylaldoxime (5-Me-saloxH2 ) donne un complexe hexanucléaire chiral de manganèse(III) [MnIII63 -O)2 (5-Me-salox)6 (S-mandélato)2 (EtOH)6 ]. La structure est constituée de deux sous-unités neutres {Mn33 -O)(5-Me-salox)3 (S -mandélato)(EtOH)3 } triangulaires assemblées tête-bêche par deux atomes d’oxygène phenoxo et deux atomes d’oxygène oximato μ3  des groupes oxime déprotonés des ligands. L’étude magnétique de ce complexe hexanucléaire chiral de manganèse(III) révèle un comportement SMM avec une barrière d’énergie de la relaxation lente de l’aimantation égale à 35K. Prenant en compte les caractéristiques structurales, la variation thermique de la susceptibilité magnétique donne un bon accord avec les données expérimentales en considérant une interaction J 1 =+0,37cm−1 dans les sous-unités triangulaires {Mn33 -O)(5-Me-salox)3 (S -mandélato)(EtOH)3 } et une interaction antiferromagnétique J 2 =−0,70cm−1 entre les deux sous-unités.

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Keywords : Manganese(III), Chiral, Salicylaldoxime, Mandelic acid, Magnetism, Single-molecule magnets

Mots clés : Manganèse(III), Chiral, Salicylaldoxime, Acide mandélique, Magnétisme, Molécule-aimant




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