Exchange Couplings and Magneto-Structural Correlations of Trinuclear MII-UIV-MII (MII=Co, Ni, Cu) Complexes - CEA - Université Paris-Saclay Accéder directement au contenu
Article Dans Une Revue European Journal of Inorganic Chemistry Année : 2024

Exchange Couplings and Magneto-Structural Correlations of Trinuclear MII-UIV-MII (MII=Co, Ni, Cu) Complexes

Résumé

The magnetic properties of the trinuclear Schiff base complexes M2UL7 (M-II=Co, Ni, Cu; L-7=N,N'-bis(3-hydroxysalicylidene)-2,2-dimethyl-1,3-propanediamine), exhibiting the [M(mu-O)(2)](2)U core structure (3d-5 f-3d subsystem), have been investigated theoretically using scalar relativistic ZORA/DFT computations combined with the broken symmetry (BS) approach. The calculated coupling constants J(MU) between the adjacent M1-U and M2-U agree with the observed ferromagnetic (Ferro) character observed in the case of the Cu2UL7 complex, the antiferromagnetic (AF) character of the Ni2UL7 one is consistent with the experimentally observed AF behaviour for Co2UL7. The structural parameters, in particular the M-U distances and the M-O-b-U angles, as well as the electronic factors driving the superexchange couplings are discussed. The bond orders and the magnetic molecular orbital analyses reveal that the U(5 f) covalent contribution to the bonding within the M-O-U coordination is more important in the Co2UL7 and Ni2UL7 complexes than in the Cu2UL7 congener, thus favouring AF coupling between the transition metal and the uranium magnetic centers, in the first complexes. The analyses are supported by the study of the mixed ZnMUL7 and M2ThL7 systems, where the Co-II (3d(7)) and Ni-II (3d(8)) paramagnetic ions are replaced by the diamagnetic Zn-II(3d(10)) one, whereas in the second complex, the U-IV(5f(2)) paramagnetic center is replaced by the diamagnetic Th-IV(5f(0)) one. The Natural Populations Analyses confirm the crucial role of spin delocalization that is at work in favour of the AF vs. Ferro magnetic character of the M-U-M (M=Ni, Co) and Cu-U-Cu coordination, respectively.
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mercredi 25 septembre 2024
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hal-04576827 , version 1 (25-06-2024)

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Lotfi Belkhiri, Rémi Maurice, Boris Le Guennic, Abdou Boucekkine, Michel Ephritikhine. Exchange Couplings and Magneto-Structural Correlations of Trinuclear MII-UIV-MII (MII=Co, Ni, Cu) Complexes. European Journal of Inorganic Chemistry, 2024, 27 (14), pp.e202300788. ⟨10.1002/ejic.202300788⟩. ⟨hal-04576827⟩
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