• A five-coordinate manganese(iii) complex of a salen type ligand with a positive axial anisotropy parameter D

    • Sergiu Shova
    • Inorganic Polymers Department, “Petru Poni” Institute of Macromolecular Chemistry
    • Angelica Vlad
    • Inorganic Polymers Department, “Petru Poni” Institute of Macromolecular Chemistry
    • Maria Cazacu
    • Inorganic Polymers Department, “Petru Poni” Institute of Macromolecular Chemistry
    • J. Krzystek
    • National High Magnetic Field Laboratory, Florida State University
    • Lukas Bucinsky
    • Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology
    • Martin Breza
    • Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology
    • Denisa Darvasiová
    • Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology
    • Peter Rapta
    • Institute of Physical Chemistry and Chemical Physics, Slovak University of Technology
    • Joan Cano
    • Institut de Ciència Molecular, Universitat de València
    • Joshua Telser
    • Department of Biological, Chemical and Physical Sciences, Roosevelt University
    • Vladimir B. Arion
    • Department of Inorganic Chemistry, Faculty of Chemistry, University of Vienna
  • A new high-spin d4 roughly trigonal–bipyramidal (TBP) manganese(III) complex with a salen type ligand (H2L), namely MnL(NCS)·0.4H2O, has been synthesised and characterised by elemental analysis, ESI mass spectrometry, IR and UV-vis spectroscopy, and spectroelectrochemistry. X-ray diffraction analysis revealed an axial compression of the approximate TBP. Temperature dependent magnetic susceptibility and variable-temperature variable-field (VTVH) magnetisation measurements, as well as high-frequency and -field EPR (HFEPR) spectroscopy, were used to accurately describe the magnetic properties of this complex and, in particular, determine the spin Hamiltonian parameters: g-values and the zero-field splitting (ZFS) parameters D and E. The HFEPR spectra allowed the extraction of fourth order ZFS parameters. Quantum chemical calculations reproduced well the electronic and geometric structures of this unusual complex and, in particular, its electronic absorption spectrum along with the spin Hamiltonian parameters.

  • PDF

  • http://phaidra.univie.ac.at/o:561933

  • Article

  • Published Version

  • Dalton Transactions

  • 2017

  • 46

  • 35

  • 11817-11829

  • Royal Society of Chemistry (RSC)

  • English

  • Open access

  • SK02/2013 – Österreichischer Austauschdienst (OeAD)

  • RO01/2014 – Österreichischer Austauschdienst (OeAD)

  • 1477-9226