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Related Experiment Videos

High-spin chloro mononuclear MnIII complexes: a multifrequency high-field EPR study.

Claire Mantel1, Hongyu Chen, Robert H Crabtree

  • 1High Magnetic Field Laboratory of Grenoble, HMFL, CNRS-MPI UPR 5021 BP 166, F 38042 Grenoble 9, France.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|April 1, 2005
PubMed
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New chloromanganese (III) complexes, [Mn(terpy)(Cl)3] and [Mn(Phterpy)(Cl)3], exhibit Jahn-Teller distortion. Their electronic properties were studied using multifrequency EPR, revealing correlations between distortion, magnetic properties, and ligand field strength.

Area of Science:

  • Inorganic Chemistry
  • Coordination Chemistry
  • Materials Science

Background:

  • Six-coordinated chloromanganese (III) complexes with N-tridentate ligands are synthesized.
  • These complexes are analogous to previously studied mononuclear azide and fluoride Mn(III) complexes.
  • High-spin Mn(III) complexes are known to exhibit Jahn-Teller distortion.

Purpose of the Study:

  • To isolate and structurally characterize two new chloromanganese (III) complexes: [Mn(terpy)(Cl)3] (1) and [Mn(Phterpy)(Cl)3] (2).
  • To investigate the electronic properties of these complexes using multifrequency electron paramagnetic resonance (EPR).
  • To correlate structural distortions with electronic and magnetic properties.

Main Methods:

  • Synthesis and isolation of chloromanganese (III) complexes.

Related Experiment Videos

  • X-ray crystallography for structural characterization.
  • Multifrequency EPR spectroscopy (190-475 GHz) in the solid state at low temperatures (5-15 K).

    • Main Results:

    • Complexes 1 and 2 show a characteristic Jahn-Teller distortion with tetragonal elongation.
    • The sign of the axial zero-field splitting parameter (D) correlates with the distortion.
    • The magnitude of D is insensitive to anion type in rhombic complexes, unlike porphyrinic systems.
    • The [E/D] values for complexes 1 and 2 are smaller than those in related [Mn(L)(X)3] complexes.
    • The E term increases as equatorial ligand-field strength decreases.

    Conclusions:

    • The study confirms previous findings on Jahn-Teller distorted Mn(III) complexes.
    • Electronic properties are sensitive to ligand field strength and structural distortions.
    • The results provide insights into the relationship between structure and magnetic properties in manganese complexes.