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Article Dans Une Revue Dalton Transactions Année : 2022

Structural determinations and magnetic properties of a “chiral at metal” complex and its resulting [Cu–Ln] 2 compounds

Résumé

A chiral trianionic ligand possessing one amide, one imine, two phenol functions and one asymmetric carbon atom into its diamino chain reacts with CuII ions to yield anionic [LCu]− units that crystallize in a non-centrosymmetric space group as infinite 1D zig-zag chains in which a transmission of chirality to the CuII ion is effective. The distorted square planar environment of the CuII ion is large enough to induce the presence of a stereogenic CuII centre. Further reaction with LnIII ions in presence of ancillary ligands does not preserve such an arrangement but yields a tetranuclear complex made of two [LCu–Ln] units in a head-to-tail position. The tetranuclear [LCu–Ln]2 complexes made with the racemic and chiral LCu units crystallize in different space groups, so that racemization does not occur. The structural determinations confirm that a symmetry centre is present in the two structures, except for the methyl groups linked to the chiral carbon atoms, which appear as disordered in the (S-S) tetranuclear entity. Such an arrangement implies a conformation change of the diamino chain linked to the CuII ion in one [LCu–Ln] unit of the (S-S) entity, and cancels any chirality contribution of the CuII ions, as in the meso compound. Ferromagnetic Cu–Ln interactions, resulting from an alternate distribution of the CuII and LnIII ions, are the only ones to be active. Eventually the micro-Squid studies confirm that the hysteresis loops of the corresponding racemate and chiral tetranuclear [LCu–Dy]2 entities are slightly different.
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Dates et versions

hal-03592049 , version 1 (01-03-2022)

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Jean-Pierre Costes, Carine Duhayon, Laure Vendier, Wolfgang Wernsdorfer. Structural determinations and magnetic properties of a “chiral at metal” complex and its resulting [Cu–Ln] 2 compounds. Dalton Transactions, 2022, 51 (7), pp.2805-2814. ⟨10.1039/D1DT04249A⟩. ⟨hal-03592049⟩
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