Synthesis, structural, magnetic and high frequency EPR studies on a hexametallic Fe(III) complex with a highly rhombic S = 5 ground state

Paul Cooper, Floriana Tuna, Muralidharan Shanmugam, Lorenzo Sorace, Sarah L. Heath, David Collison, Eric J L McInnes, Richard E P Winpenny

    Research output: Contribution to journalArticlepeer-review

    Abstract

    The synthesis, crystal structure and magnetic properties of the hexametallic Fe(III) cluster [Fe6III O2 (OH)2 {(C4 N2 H2 SMe)2 C (OH) O}2 (t BuCO2)10] (1) are reported. Compound 1 was prepared by reaction of mixed-valent [Fe3O(tBuCO2)6(py) 3] with one equivalent of the new ligand di-2-(4-methylthio)pyrimidyl ketone (DTPK) in MeCN solution. Compound 1 consists of a planar array of six Fe(III) ions comprising two [Fe3(μ3-O)]7+ subunits that are related by an inversion centre and linked at two of their apices, each via one μ-hydroxide and two μ-carboxylate groups. Variable temperature magnetic susceptibility and low temperature magnetization measurements show a well isolated S = 5 electronic spin ground state. Variable temperature W-band EPR measurements on a polycrystalline sample give well resolved spectra and simulations confirm a negative zero-field splitting of D = -0.224 cm-1 but also reveal a very rhombic nature (E/|D| = 0.27). Although 1 has a well isolated S = 5 ground state with a negative magnetic anisotropy, it is not a SMM due to this large rhombicity. © 2008 Elsevier B.V. All rights reserved.
    Original languageEnglish
    Pages (from-to)3663-3668
    Number of pages5
    JournalInorganica Chimica Acta
    Volume361
    Issue number12-13
    DOIs
    Publication statusPublished - 1 Sept 2008

    Keywords

    • HF-EPR
    • High spin ground states
    • Iron clusters
    • Magnetic studies

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