Electronic structure and magnetic properties of naphthalene- and stilbene-diimide-bridged diuranium(V) complexes: a theo
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ORIGINAL PAPER
Electronic structure and magnetic properties of naphthaleneand stilbene-diimide-bridged diuranium(V) complexes: a theoretical study Seddik Boucenina 1,2 & Lotfi Belkhiri 1 & Samir Meskaldji 1,3 & Roberto Linguerri 2 & Gilberte Chambaud 2 & Abdou Boucekkine 4 & Majdi Hochlaf 2 Received: 25 May 2020 / Accepted: 17 September 2020 / Published online: 24 September 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract The magnetic exchange coupling between two diuranium(V) ions exhibiting the 5f1-5f1 configuration in diimide-bridged complexes [Cp3UV]2(μ-L) (L = stilbene-, naphthalene-diimide) has been investigated theoretically using relativistic ZORA/DFT calculations. Using two different hybrid PBE0 and B3LYP functionals, combined with the broken symmetry (BS) approach, we found that the BS states of both naphthalene and stilbene complexes have lower energy than the corresponding high-spin (HS) triplet ones. The B3LYP/BS estimated exchange coupling J constants (− 16.1 vs. − 9.0 cm−1 respectively for the naphthalene and stilbene complexes) corroborate well with those obtained previously for other pentavalent diuranium(V) diimide-bridged systems. The computed J value is found to be sensitive to π-network linking the two magnetic U(V) centers. The natural spin density distributions and molecular orbital analyses explain well the antiferromagnetic character of these compounds and clarify the crucial role of the π aromatic spacer in promoting spin polarization and delocalization favoring the magnetic coupling. Furthermore, the effective involvement of the 6d/5f metal orbitals in metal-ligand bonding plays an important role for the magnetic communication between the two active U(V) 5f electrons.
Keywords Diuranium(V) complexes . Magnetic exchange coupling . ZORA/B3LYP . Broken symmetry
Introduction Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00894-020-04552-9) contains supplementary material, which is available to authorized users. * Lotfi Belkhiri [email protected] * Majdi Hochlaf [email protected] 1
Laboratoire de Physique Mathématique et Subatomique LPMS, Département de Chimie, Université des Frères Mentouri, 25017 Constantine, Algeria
2
Université Gustave Eiffel, COSYS/LISIS, 5 Bd Descartes, 77454 Champs sur Marne, France
3
Ecole Normale Supérieure de l’Enseignement Technique – ENSET, 21000 Skikda, Algeria
4
Univ Rennes, ISCR UMR 6226 CNRS Université Rennes 1, Campus de Beaulieu, F-35042 Rennes Cedex, France
During the past three decades, the magnetic properties of binuclear actinide complexes attracted attention, at both the experimental and theoretical levels [1–10]. Indeed, their ability to support exotic metal-ligand bonding motifs, large spin– orbit coupling, and anisotropy barriers allows potential applications in the field of single-molecule magnets (SMM), as pointed out in several recent reviews [1–6, 11–14]. In particular, the unique features of actinide-containing molecules may be exploited for the design
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