By Design: A Macrocyclic 3d−4f Single-Molecule Magnet with Quantifiable Zero-Field Slow Relaxation of Magnetization - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2013

By Design: A Macrocyclic 3d−4f Single-Molecule Magnet with Quantifiable Zero-Field Slow Relaxation of Magnetization

Résumé

Rational modification of the equatorially bound tetranucleating macrocycle in the previously reported SMM complex of the propylene linked macrocycle [CuII 3TbIII(LPr)]-(NO3)2, to a new butylene linked analogue, is shown to tune the ligand field imposed on the encapsulated CuII3TbIII cluster. This results in apical binding of two, rather than one, nitrate ions to the oblate TbIII ion, giving enhanced uniaxial anisotropy and SMM properties despite the low symmetry of the Tb(III) site. The resulting complex, [CuII 3TbIII(LBu)-(NO3)2(MeOH)(H2O)](NO3)*3H2O, is the first example of a macrocyclic 3d−4f single-molecule magnet that exhibits quantifiable relaxation of magnetization in zero dc field (Δeff/kB =19.5(5) K; τ0 = 3.4 × 10−7 s). This SMM complex of this new, larger, tetranucleating macrocycle was prepared by the template method from the 3:3:3:1 reaction of 1,4-diformyl-2,3-dihydroxybenzene/diaminobutane/copper(II) acetate/terbium(III) nitrate. Similarly, the analogues, Zn3Tb(LBu)(NO3)3*MeOH*H2O*DMF and [Cu3La(LBu)(NO3)2(MeOH)(H2O)2](NO3)*H2O*DMF, were prepared in order to facilitate the detailed magnetic analysis. Both copper(II) complexes were also structurally characterized, confirming the expected binding mode: lanthanide(III) ion in the central O6 pocket, and the three copper(II) ions in the outer N2O2 pockets.

Domaines

Matériaux
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Dates et versions

hal-00803313 , version 1 (21-03-2013)

Identifiants

Citer

Humphrey L. C. Feltham, Rodolphe Clérac, Liviu Ungur, Liviu F. Chibotaru, Annie K. Powell, et al.. By Design: A Macrocyclic 3d−4f Single-Molecule Magnet with Quantifiable Zero-Field Slow Relaxation of Magnetization. Inorganic Chemistry, 2013, 52, pp. 3236-3240. ⟨10.1021/ic302735j⟩. ⟨hal-00803313⟩

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