(Schiff-base)CuII Complexes with Phenolate-Oxygen/Chloro or -Oxygen/Azido Mixed Bridges − Syntheses, Crystal Structures and Magnetic Properties

Four new CuII complexes of formulae [Cu3(SE)2(H2O)2Cl3]Cl·6H2O (1), Cu3(SE)2(N3)4(DMF)2 (2), Cu(SE)N3·DMF (3) and Cu(SE)N3·Cu(SE)N3 (4) with tridentate Schiff-base ligands SE−, derived from condensation of N,N-dimethylethylenediamine with salicylaldehyde, have been synthesised and characterised by IR spectroscopy, X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Complex 1 has an alternating phenoxy- and chloro-bridged 1D chain structure. Complex 2 possesses trinuclear units in which the CuII ions are bridged by single end-on (µ-1,1) azido ligands. Uniformly spaced 1D chains with end-to-end (µ-1,3) azido bridges are found in 3 and 4. As expected, complexes 1 and 2 exhibit antiferromagnetic and ferromagnetic exchange, respectively. Compounds 3 and 4 show unusual ferromagnetic coupling though the 1,3-azido pathways. Theoretical simulations have been carried out in order to evaluate the magnitude of the magnetic exchange and the magneto-structural correlation has been investigated. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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