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Density functional theory study of the magnetic coupling interaction in a series of binuclear oxalate complexes

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Abstract

Magnetic couplings in oxalate-bridged binuclear complexes, namely five isomers of [(VO)2(ox)(SCN)6]4−, trans-(equatorial, equatorial), cis-(equatorial, equatorial), trans-(axial, axial), cis-(axial, axial), and (axial, equatorial), as well as [Cr2(ox)(SCN)8]4−, [Fe2(ox)(SCN)8]4−, [CrFe(ox)(SCN)8]4−, [Fe2(ox)5]4−, [Cr2(ox)5]4−, [Ni2(ox)5]6−, and [Cu2(ox)(C12H8N2)2]2+, were calculated with the broken symmetry approach. Predominant antiferromagnetic coupling is found in almost all investigated complexes, except in [CrFe(ox)(SCN)8]4−. The best agreement with experimental values for the exchange coupling constants were obtained at the B3LYP level of theory, whereas the non-hybrid functionals gave the best trend for the investigated vanadium complexes. The linear relationship between coupling constant and (ε 2  − ε 1)2 as well as linear dependence of J and the square of overlap integral of magnetic orbitals was estimated.

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Acknowledgments

This work was financially supported by the Serbian Ministry of Education and Science through the Grant No. 172035 and is part of COST CMST Action CM1002 (“COnvergent Distributed Environment for Computational Spectroscopy (CODECS)”).

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Authors and Affiliations

  1. Center for Chemistry, Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoševa 12, P.O. Box 815, 11001, Belgrade, Serbia

    Marko Perić, Matija Zlatar & Sonja Grubišić

  2. Faculty of Chemistry, University of Belgrade, Studentski trg 16, P.O. Box 158, 11001, Belgrade, Serbia

    Maja Gruden-Pavlović

Authors
  1. Marko Perić
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  2. Matija Zlatar
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  3. Maja Gruden-Pavlović
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  4. Sonja Grubišić
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Correspondence to Sonja Grubišić.

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Perić, M., Zlatar, M., Gruden-Pavlović, M. et al. Density functional theory study of the magnetic coupling interaction in a series of binuclear oxalate complexes. Monatsh Chem 143, 569–577 (2012). https://doi.org/10.1007/s00706-011-0705-1

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  • DOI: https://doi.org/10.1007/s00706-011-0705-1

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