Synthesis and properties of dinuclear μ-oxodiiron(III) complexes of amide-based macrocyclic ligands

Sushil Kumar, Shefali Vaidya, Michael Pissas, Yiannis Sanakis, Rajeev Gupta

    Research output: Contribution to journalArticlepeer-review

    8 Scopus citations

    Abstract

    We report the syntheses, structural, Mössbauer, magnetic, and redox characterization of a series of μ-oxido-bridged diiron(III) complexes in a set of 13-membered amide-based macrocyclic ligands that contain electron-donating and -withdrawing substituents (-H, -Cl, and -CH 3) on the ligand periphery. For all three complexes, the Mössbauer spectra indicate that two iron sites are indistinguishable, a fact that is well supported by X-ray crystallographic results. The three complexes exhibit almost identical isomer shifts but distinctively different quadruple splitting values. The variable-temperature magnetic susceptibility measurements show that the unsupported single μ-oxido group mediates a strong antiferromagnetic coupling between two Fe III ions. The three diiron complexes show quite different magnetic coupling (J = 191, 194, and 230 cm -1, respectively; H iso = J S 1·S 2) that has been related to the structural differences. We also show that the electron-donating and -withdrawing substituents present on the ligands influence the redox properties.

    Original languageBritish English
    Pages (from-to)5525-5533
    Number of pages9
    JournalEuropean Journal of Inorganic Chemistry
    Issue number33
    DOIs
    StatePublished - Nov 2012

    Keywords

    • Iron
    • Macrocyclic ligands
    • Magnetic properties
    • Mössbauer spectra

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