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The synthesis, structural, and magnetic characterization of a novel neutral copper(II) hexanuclear complex [Cu6(en)4(OCH2CH2O)2(pyox)4]·3eg·en·12H2O (1) was investigated [en = ethylenediamine, eg = ethylene glycol, and H2pyox = 4-(1H-pyrazole-4-yl)phenylene-N-oxamic acid]. The crystal structure of 1, obtained by the single-crystal X-ray diffraction technique, revealed that the hexacopper(II) complex is built from two linear tricopper(II) complex subunits. Each subunit contains two [Cu(en)]2+ moieties connected to a [Cu(OCH2CH2O)] unit by two pyox2− ligands acting as μ-κN:κN′ bridges, as well as a [OCH2CH2O]2− ligand, which is ultimately found in the μ3-κO,O′:κO:κO′ coordination form. The subunits are connected via the amide portion of the pyox2− ligand, linked to copper atoms in the other subunit. They occupy the apical coordination positions, leading the trinuclear copper(II) segments to be almost perpendicular. The structural, chemical, and spectroscopic characterizations evidenced that ethylene glycol acted both as a solvent and a reactant upon deprotonation, forming the –OCH2CH2O– ligand due to the basic crystallization environment. DC magnetic studies revealed a strong antiferromagnetic interaction between the copper atoms within the trinuclear subunits, influenced by alkoxide and pyrazolate bridging ligands. Our findings offer new insights into the structural and magnetic properties of copper(II) complexes, enhancing the understanding of metal–ligand interactions in supramolecular chemistry.

The synthesis, crystal structure and magnetic properties of the coordination polymers of formula [EDAP{Li6(H2O)8[(Cu2(μ-mpba)2)2(H2O)2]}]n (1) and [(EDAP)2{K(H2O)4[Cu2(μ-mpba)2(H2O)2]}Cl·2H2O]n (2), in which mpba = N,N′-1,3-phenylenebis(oxamate) and EDAP2+ = 1,1′-ethylenebis(4-aminopyridinium) are described. Both compounds have in common the presence of the [Cu2(mpba)2]4− tetraanionic unit which is a [3,3] metallacyclophane motif in which the copper(II) ions are five-coordinate in a distorted square pyramidal surrounding. The complex anion in 1 is dimerized through double out-of-plane copper to outer carboxylate-oxygen atoms resulting in the centrosymmetric tetracopper(II) fragment [Cu4(μ-mpba)4(H2O)2]8− which act as a ligand toward six hydrated lithium(I) cations leading to anionic ladder-like double chains whose charge is neutralized by the EDAP2+ cations. In the case of 2, each dicopper(II) entity acts as a ligand towards tetraquapotassium(I) units to afford anionic zig zag single chains of formula {K(H2O)4[Cu2(μ-mpba)2(H2O)2]}n3n− plus EDAP2+ cations and non-coordinate chloride anions. Cryomagnetic measurements on polycrystalline samples 1 and 2 show the occurrence of ferromagnetic interactions between the copper(II) ions across the –Namidate–(C–C–C)phenyl–Namidate– exchange pathway [J = +10.6 (1) and +8.22 cm−1 (2)] and antiferromagnetic ones through the double out-of-plane carboxylate-oxygen atoms [j = −0.68 cm−1 (1), the spin Hamiltonian being defined as H = − J ( S C u 1 · S C u 2 + S C u 2 i · S C u 1 i ) − j ( S C u 2 · S C u 2 i ) ].