The synthesis, structure and SOD-like behaviors of a μ-imidazolato-dicopper(II) complex with a binucleating hexaazamacrocycle

Abstract

The synthesis, crystal structure and magnetic properties of the imidazolate-bridged dinuclear copper(II) complex [LCu 2(Im)(DMSO) 2](ClO 4) 3(DMSO), where ImH is imidazole, and L is 3, 6, 9, 17, 20, 23-hexaazatricyclo[23.3.1.1 11,13]triaconta-1(29), 11(30), 12, 14, 25(26), 27-hexaene, have been studied. Single crystal X-ray diffraction determination reveals the distorted tetragonal pyramid geometries of the imidazolate bridged dicopper(II) center are incorporated within the binucleating macrocycle. Both copper atoms are five-coordinated by four basal nitrogen atoms (three from the macrocycle and one from the imidazolate) and one oxygen atom from the DMSO molecule. Two coordinated DMSO molecules are situated at the same side of the macrocycle. The Cu–Cu separation in the complex is 5.93 Å. Magnetic measurements and ESR spectroscopy studies exibit an antiferromagnetic exchange interaction with a coupling constant of J= − 26.94 cm −1. Investigations on the pH-dependent ESR of the title compound in frozen 50% aqueous DMSO solution confirm the existence of the bridged cation [LCu 2(Im)] 3+ as a major species in solution mainly in the range 5.2⩽pH⩽11.5. The imidazolate bridge is broken in the pH range of 5.2–3.3, which is close to that for the native enzyme.