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A relativistic DFT study of magnetic exchange coupling in ketimide bimetallic uranium(IV) complexes

  • Samir Meskaldji
  • Abdellah Zaiter
  • Lotfi BelkhiriEmail author
  • Abdou BoucekkineEmail author
Regular Article
Part of the following topical collections:
  1. Barone Festschrift Collection

Abstract

Magnetic exchange couplings in bis(ketimide) binuclear UIV/UIV complexes [Cp′2UCl]2(μ-ketimide) diuranium(IV) and [(C5H5)2(Cl)An]2(μ-ketimide) (Cp′ = C5Me4Et; ketimide = N=CMe-(C6H4)-MeC=N) have been investigated computationally using relativistic density functional theory (DFT) combined with the broken symmetry (BS) approach. Using the B3LYP hybrid functional, the BS ground state of these UIV/UIV 5f 2–5f 2 complexes has been found of lower energy than the high spin (HS) quintet state, indicating an antiferromagnetic character (estimated coupling constant |J| < 5 cm−1) which has not yet been evidenced unambiguously experimentally. On the contrary, the BP86 GGA functional overestimates greatly the antiferromagnetic character of the complexes (|J| > 100 cm−1). As recently reported for para-bis(imido) [(C5H5)3U]2(μ-imido) uranium(V) complex, spin polarization is mainly responsible for the antiferromagnetic coupling through the π-network orbital pathway within the bis(ketimide) bridge. Furthermore, spin polarization is exalted by the combined roles of the 5f metal orbitals and of the π-conjugated ketimide bridging ligand which permit electronic communication between the two uranium atoms albeit separated by a distance of the order of 10 Å. The MO analysis clarifies which MOs contribute to the antiferromagnetic coupling in the binuclear complexes under consideration and brings to light the 5f orbitals driving contribution.

Keywords

Ketimide biuranium(IV) complexes Magnetic exchange coupling ZORA/B3LYP Broken symmetry 

Notes

Acknowledgments

Financial support from the Algerian National Administration of Scientific Research NASR-ANDRU (PNR Grant No. 8/u250/4169) is gratefully acknowledged. Computing facilities were provided by IDRIS Computing Centre of CNRS.

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Authors and Affiliations

  1. 1.URCHEMS, Université Mentouri de ConstantineConstantineAlgeria
  2. 2.ENSETSkikdaAlgeria
  3. 3.Laboratoire Sciences chimiques de Rennes, UMR CNRS 6226Rennes CedexFrance

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