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Russian Chemical Bulletin

, Volume 59, Issue 4, pp 717–723 | Cite as

Synthesis, structures, and magnetic properties of crystals of dinuclear copper(II) and cobalt(II) complexes with 3-(3,5-dimethylpyrazol-1-yl)-6-R-1,2,4,5-tetrazines

  • E. V. Cherdantseva
  • D. V. Starichenko
  • P. A. Slepukhin
  • R. I. Ishmetova
  • Yu. N. Shvachko
  • A. V. Korolev
  • G. L. Rusinov
  • V. V. Ustinov
  • A. I. Matern
  • V. N. Charushin
Full Articles

Abstract

Dinuclear complexes of CuII with 3-(3,5-dimethylpyrazol-1-yl)-6-(2-hydroxyethylami-no)-1,2,4,5-tetrazine (1) and CoII with 3-(3,5-dimethylpyrazol-1-yl)-6-(piperidin-1-yl)-1,2,4,5- tetrazine (2) were synthesized and structurally characterized, and the magnetic (SQUID) and resonance (EPR) properties of van der Waals crystals based on these complexes were studied. Unusual behavior of the effective magnetic moment μeff(T) is observed at T < 60 K. A nonmonotonic increase in μeff(?) for 1 (s~6 %) and a 20% reduction of μeff(?) for 2 have a common origin and are due to the influence of spin-orbital coupling on the character of the splitting between the t2g and eg levels of the central ion. Distortions of the coordination site “switch on” a positive (1) or negative (2) contribution of the orbital magnetic moment near 6 K. Irreversible temperature behavior of μeff(T) in the heating and cooling regimes in the vicinity of 60 K suggests that the character of structural distortions and the magnetic properties are related to ligand geometry. This factor plays a significant role in crystal engineering of magnetoactive structures with polynitrogen ligands.

Key words

dinuclear complexes 3-(3,5-dimethylpyrazol-1-yl)-6-R-1,2,4,5-tetrazines X-ray analysis EPR spectroscopy SQUID magnetometry spin magnetism 

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Copyright information

© Springer Science+Business Media, Inc.  2010

Authors and Affiliations

  • E. V. Cherdantseva
    • 1
  • D. V. Starichenko
    • 2
  • P. A. Slepukhin
    • 3
  • R. I. Ishmetova
    • 3
  • Yu. N. Shvachko
    • 2
  • A. V. Korolev
    • 2
  • G. L. Rusinov
    • 3
  • V. V. Ustinov
    • 2
  • A. I. Matern
    • 1
  • V. N. Charushin
    • 3
  1. 1.B. N. Yeltsin Ural State Technical UniversityEkaterinburgRussian Federation
  2. 2.Institute of Metal PhysicsUral Branch of the Russian Academy of SciencesEkaterinburgRussian Federation
  3. 3.I. Ya. Postovskii Institute of Organic SynthesisUral Branch of the Russian Academy of SciencesEkaterinburgRussian Federation

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