Electronic Structure and Magneto-Structural Correlations Study of Cu₂UL Trinuclear Schiff Base Complexes: A 3d-5f-3d...

The magnetic properties of trinuclear Schiff base complexes M₂AnLⁱ (M^II = Zn, Cu; An^IV = Th, U; Lⁱ = Schiff base; i = 1-4, 6, 7, 9), exhibiting the [M(μ-O)₂]₂U core structure with adjacent M1···U and M2···U and next-adjacent M1···M2 interactions, featuring 3d-5f-3d subsystems, have been investigated theoretically using relativistic ZORA/B3LYP computations combined with the broken symmetry (BS) approach. Bond order and natural population analyses reveal that the covalent contribution to the bonding within the Cu-O-U coordination is important thus favoring superexchange coupling between the transition metal and the uranium magnetic centers. The calculated coupling constants J_CuU between the Cu and U atoms, agree with the observed shift from the antiferromagnetic (AF) character of the L^1,2,3,4 complexes to the ferromagnetic (ferro) of the L^6,7,9 ones. The structural parameters, i.e., the Cu···U distances and the Cu-O-U angles, as well as the electronic factors driving the magnetic couplings are discussed. The analyses are supported by the study of the mixed ZnCuULⁱ and Cu₂ThLⁱ systems, where in the first complex the Cu^II (3d⁹) ion is replaced by the diamagnetic Zn^II (3d¹⁰) one, whereas in the second complex the U^IV (5f²) paramagnetic center is replaced by the diamagnetic Th^IV (5f⁰) one.