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

Xiaozhou Ma, Elizaveta A. Suturina, Mathieu Rouzières, Mikhail Platunov, Fabrice Wilhelm, Andrei Rogalev, Rodolphe Clérac, Pierre Dechambenoit

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21 Citations (SciVal)
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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 ferromagnetic 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 TC molecule-based magnets.

Original languageEnglish
Pages (from-to)7721-7725
Number of pages5
JournalJournal of the American Chemical Society
Issue number19
Early online date26 Apr 2019
Publication statusPublished - 15 May 2019

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry


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