Ferromagnetic Coupling in a New Copper(II) Schiff Base Complex with Cubane Core: Structure, Magnetic Properties, DFT Study and Catalytic Activity

A new tetranuclear complex, [Cu4L4]center dot 2H(2)O (1), has beets synthesizer from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligand 4-chloro-2-[(E)-(2-hydroxy-ethylimino)methyl]phenol(H2L) Single-crystal X-ray diffraction studies reveal that complex 1 consists of a Cu4O4 cubane core where the four copper(II) centers are linked by mu(3)-alkoxo bridges. Each Cu-II ion assumes a distorted square-pyramidal geometry with CUNO4 Chromophore Variable-temperature magnetic susceptibility data exhibit distinct ferromagnetic exchange interaction, coiroborating with the geometrical parameters of the structural unit. Theoretical calculations based on DFT method have been used to quantity the strength of the Cu center dot center dot center dot Cu magnetic interactions which help to evaluate the experimental coupling constants J(1) = +64.8, J(2) = +24.4 and J(3) = +3.0 cm(-1). The EPR spectroscopy also gives some insight on the ferromagnetic S = 2 ground state of 1 in addition, detailed investigations have been carried out oil the catalytic activity of the complex towards the oxidation of cycloalkanes using H2O2 as terminal oxidant. ((C) Wiley-VCH Verlag GmbH &. Co. KGaA, 69451 Weinheim, Germany, 2009)