Polynuclear 3d complexes based on potentially tetra-anionic heptadentate ligands including amido,amino and phenoxo donors: Synthesis,crystal structure and magnetic properties

The synthesis and characterization of new dinuclear Mn^III and tetranuclear Cu^II complexes, HL¹Mn(DMSO)]₂ (1) and H₂L²Cu₂(MeO)₂]₂ (2), are reported (H₄L¹ = 2-hydroxy-N-2-({2-(2-hydroxybenzoyl)amino]ethyl}amino)ethyl]benzamide and H₄L² = 2-hydroxy-N-3-({3-(2-hydroxybenzoyl)amino]propyl}(methyl)amino)propyl]benzamide). Single crystal X-ray structures have been determined for 1 and 2. In 1 only one of the two amide functions of H₄L¹ is deprotonated in addition to the phenol ones, while in 2 all the amide functions of H₄L² are protonated and none of the potential nitrogen donors (amide and amine) is involved in the coordination to copper. HL¹ and H₂L² do not play the role of compartmental ligands and do not wrap around one Mn and one Cu ion, respectively, but embrace two metal centers yielding, with the respective assistance of auxiliary DMSO and methoxo ligands, dinuclear manganese and tetranuclear copper complexes, respectively. 1 includes two well isolated Mn^III ions (Mn?Mn′ = 7.33 Å) that do not interact magnetically. The intermolecular Mn?Mn″ distance along the 1D chains (10.17 Å) is also too large to allow extended magnetic interactions. The pairwise magnetic interactions between the copper(II) ions in the tetranuclear complex 2 are so large that the χ_MT product is already equal to zero at room temperature, implying that the antiferromagnetic interaction is around −1000 cm⁻¹, as observed previously for di-μ-hydroxo–dicopper complexes.