Chain compounds based on paddle-wheel copper(Ii) carboxylate bearing four nitroxide radicals

Abstract

Chain compounds of paddle-wheel Cu2-clusters of 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (Hcaproxy) and 4-carboxy-2,2,6,6-tetramethylpiperidinyloxy (Hcatempo) and N,N’-bidentate ligands (L = 4,4′-bipyridine (4,4′-bpy), 1,2-bis(4-pyridyl)ethane (bpe), trans-1,2-bis(4-pyridyl)ethylene (bpel), 4,4′-dipyridyl disulfide (pds), 1,4-diazabicyclo[2.2.2]octane (dabco), and pyrazine (pyz)), [Cu2 (caproxy)4 (L)]n, and [Cu2 (catempo)4 (L)]n, were synthesized and characterized by elemental analysis, infrared and UV-vis spectra and temperature dependence of magnetic susceptibilities (4.5–300 K). The crystal structures of [Cu2 (caproxy)4 (pds)]n, [Cu2 (catempo)4 (4,4′-bpy)]n, and [Cu2 (catempo)4 (bpe)]n revealed zigzag or linear chains consisting of alternate arrangement of the dinuclear cluster bearing four nitroxide radicals and N,N’-bidentate ligand. Temperature dependence of magnetic susceptibilities showed a considerable antiferromagnetic interaction between the two copper(II) ions within the dinuclear cluster, and weak antiferromagnetic interaction between the dinuclear clusters and/or the radical and dinuclear cluster.