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Article Dans Une Revue Journal of the American Chemical Society Année : 2019

Using Redox-Active π Bridging Ligand as a Control Switch of Intramolecular Magnetic Interactions

Résumé

Intramolecular magnetic interactions in the dinuclear complexes [(tpy)Ni(tphz)Ni(tpy)] n+ (n=4, 3 and 2; tpy: terpyridine; tphz: tetrapyridophenazine) were tailored by changing the oxidation state of the pyrazine-based bridging ligand. While its neutral form mediates a weak antiferromagnetic (AF) coupling between the two S=1 Ni(II), its reduced form, tphz •-, promotes a remarkably large ferromag-netic exchange of +214(5)K with Ni(II) spins. Reducing twice the bridging ligand affords weak Ni-Ni interactions, in marked contrast to the Co(II) analogue. Those experimental results, supported by a careful examination of the involved orbitals, provide a clear understanding of the factors which govern strength and sign of the magnetic exchange through an aromatic bridging ligand, a prerequisite for the rational design of strongly coupled molecular systems and high T C molecule-based magnets.

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Matériaux
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Dates et versions

hal-02159961 , version 1 (19-06-2019)

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Xiaozhou Ma, Elizaveta Suturina, Mathieu Rouzières, Mikhail Platunov, Fabrice Wilhelm, et al.. Using Redox-Active π Bridging Ligand as a Control Switch of Intramolecular Magnetic Interactions. Journal of the American Chemical Society, 2019, 141 (19), pp.7721-7725. ⟨10.1021/jacs.9b03044⟩. ⟨hal-02159961⟩

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