Successive syntheses and magnetic properties of homodinuclear lanthanide macrocyclic complexes

A series of homodinuclear β-diketone lanthanide(III) complexes, formulated as [(acac)₄Ln₂(L1)] (Ln³⁺ = Dy³⁺ (1), Tb³⁺ (2), and Gd³⁺ (3), respectively) were first synthesized based on a closed-macrocyclic ligand (H₂L1) derived from the [2 + 2] cyclocondensation of 4-tert-butyl-2,6-diformylphenol and o-phenylenediamine in the presence of lanthanide acetylacetonates. Subsequently, by using the above compounds as building blocks to assemble directly with another Schiff base ligand, N,N'-bis(5-chlorosalicylidene)-o-phenylenediamine (H₂L2), three new homodinuclear sandwich-type lanthanide complexes with the general formula [Ln₂(L1)(L2)₂] (Ln³⁺ = Dy³⁺ (4), Tb³⁺ (5), and Gd³⁺ (6), respectively) were further designed and prepared. Single-crystal X-ray analyses show that the central Ln³⁺ ion adopts a distorted square antiprism conformation with D_4d local symmetry. Magnetic studies reveal ferromagnetic interaction between Dy³⁺ and Tb³⁺ centres and zero-field slow relaxation of magnetization for Dy complexes 1 and 4. The corresponding magneto-structural correlations of SMMs 1 and 4 were further discussed by theoretical calculations and with experimental outcomes.