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High-frequency and -field electron paramagnetic resonance of high-spin manganese(III) in axially symmetric coordination complexes

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An Erratum to this article was published on 01 March 2002

Abstract

High-frequency and -field electron paramagnetic resonance (HFEPR) has been used to study several complexes of high-spin manganese(III) (3d4,S = 2): [Mn(Me2dbm)X] and [Mn(OEP)X] (X = Cl−, Br−), where Me2dbm− is the anion of 4,4′-dimethyldibenzoylmethane and OEP2− is the dianion of 2,3,7,8,12,13,17,18-octaethylporphine. These non-Kramers (integer spin) systems are not EPR-active with conventional magnetic fields and microwave frequencies. However, use of fields up to 15 T in combination with multiple frequencies in the range of 95–550 GHz allows observation of richly detailed EPR spectra. Analysis of the field- and frequency-dependent HFEPR data allows accurate determination of the following spin Hamiltonian parameters for these complexes: [Mn(Me2dbm)Cl],D = −2.45(3) cm−1; [Mn(Me2dbm)Br],D = −1.40(2) cm−1; [Mn(OEP)Cl],D = −2.40(1) cm−1; [Mn(OEP)Br],D = −1.07(1) cm−1 (E ≈ 0, andg ≈ 2.0 in all cases). Comparison of structural data with the electronic parameters for these and related complexes shows quantitatively the effects of axial and equatorial ligation on the electronic structure of Mn(III). These high-spin complexes can be employed as building blocks in the construction of single-molecule magnets. Thus the accurate determination and understanding of the electronic properties, best obtainable by HFEPR, of these monomeric units is important in understanding and improving the properties of the polynuclear single-molecule magnets which can be formed from them.

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Author notes

  1. G. Christou

    Present address: Department of Chemistry, University of Florida, Gainesville, Florida, USA

Authors and Affiliations

  1. Center for Interdisciplinary Magnetic Resonance, National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida, USA

    J. Krzystek & L. C. Brunel

  2. Chemistry Program, Roosevelt University, Chicago, Illinois, USA

    J. Telser

  3. Department of Chemistry, University of California at San Diego, La Jolla, California, USA

    M. J. Knapp & D. N. Hendrickson

  4. Department of Chemistry, Indiana University, Bloomington, Indiana, USA

    G. Aromí & G. Christou

  5. Department of Chemistry, University of Florida, Gainesville, Florida, USA

    A. Angerhofer

Authors
  1. J. Krzystek
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  2. J. Telser
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  5. G. Aromí
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  6. G. Christou
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Correspondence to J. Krzystek.

Additional information

An erratum to this article is available at http://dx.doi.org/10.1007/BF03170529.

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Krzystek, J., Telser, J., Knapp, M.J. et al. High-frequency and -field electron paramagnetic resonance of high-spin manganese(III) in axially symmetric coordination complexes. Appl. Magn. Reson. 21, 571–585 (2001). https://doi.org/10.1007/BF03162430

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