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Quantum-chemical modeling of exchange coupling in the magnetic sublattice of bifunctional compounds containing heterometallic complexes of 3d and 4d metals with oxalate and dithiooxamide ligands

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Abstract

To find components of the magnetic sub-lattice of bi-functional compounds with maximum ferromagnetic exchange coupling, quantum-chemical calculations of complexes [(L)2M1III(L)M2II(L)2]5- are performed (M1III and M2II are tri- and divalent atoms of 3d and 4d transition metals M1III (Cr, Mo) and M2II (Ni, Co, Tc, Ru, Rh, Pd), L is dithiooxamide or oxalate). Calculations of the geometric structure of the complex are performed at the B3LYP/LANL2DZ level and calculations of J constants are performed at the B3LYP/TZV level. The replacement of a divalent atom of 3d metal by a divalent atom of 4d metal leads to an increase of J, whereas the replacement of a trivalent atom of 3d metal by a trivalent atom of 4d metal does not change the value of J. It is concluded that there is a correlation of J with a total change in the spin density on the M1III and M2II metals in the complexes compared to the M13+ and M22+ isolated cations.

Quantum-chemical modeling of exchange coupling in the magnetic su-blattice of bi-functional compounds containing heterometallic complexes of 3d and 4d metals with oxalate and dithiooxamide ligands.

Sergey M. Aldoshin, KonstantinV. Bozhenko, Andrey N. Utenyshev,

By means of DFT calculations of the complexes [(L)2M1III(L)M2II(L)2]5- it is found that there is a correlation of the exchange coupling constant J (red line) with the absolute value of total SD changes in the metals when moving from isolated cations M13+ and M22+ to complexes. This fact clarifies yet another aspect of the physical meaning of J.

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Notes

  1. The structural parameters of the complexes and their symmetry are given in supplementary section.

  2. For complexes of type I with oxalate (Fig.1a) the CS of M1III consists of O(6,7,12,13,18,19); the CS of M2II consists of O(5,8,23,26,29,32). For complexes with dithiooxamide (Fig. 1b) the CS of M1III involves N(6,12,18), S(7,13,19); CS of M2II involves N(8,26,32), S(5,23,29).

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Acknowledgements

The authors express their gratitude to M.Z. Aldoshina and T.L. Krivskaya.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1, Acad. Semenov av., Chernogolovka, Moscow Region, Russia, 142432

    Sergey M. Aldoshin, Konstantin V. Bozhenko & Andrey N. Utenyshev

  2. Moscow State University of Lomonosov, Leninskie gori, GSP-1, Moscow, Russia, 119991

    Sergey M. Aldoshin & Konstantin V. Bozhenko

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Correspondence to Konstantin V. Bozhenko.

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Aldoshin, S.M., Bozhenko, K.V. & Utenyshev, A.N. Quantum-chemical modeling of exchange coupling in the magnetic sublattice of bifunctional compounds containing heterometallic complexes of 3d and 4d metals with oxalate and dithiooxamide ligands. Struct Chem 28, 965–974 (2017). https://doi.org/10.1007/s11224-016-0900-0

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