Synthesis, spectral, electrochemical and magnetic properties of new asymmetric dicopper(II) complexes bearing chemically distinct coordination sites

Abstract

Two new unsymmetrical binucleating ligands, 2-[bis(3- N, N -dimethylaminopropyl)-aminomethyl]-6-[prolin-1-yl)methyl]-4-bromophenol [H 2 L 1 ] and 2-[bis(3- N, N -dimethylaminopropyl)aminomethyl]-6-[prolin-1-yl)methyl]-4-methylphenol [H 2 L 2 ], and their dicopper(II) complexes with different exogenous bridging motifs (OAc, Br and Cl) have been prepared and characterized by spectral, electrochemical, magnetic and e.p.r. studies. Electrochemical studies indicate the presence of two irreversible reduction peaks in the cathodic region. Variable temperature magnetic susceptibility studies of the complexes show that the extent of antiferromagnetic coupling increases in the order: OAc − < Cl − < Br − . Broad isotropic or axial symmetric spectral features are observed in powder e.p.r. spectra of the complexes at 77 K. A comparison of the electrochemical and magnetic behaviour of the complexes derived from the ligands is discussed on the basis of an exogenous bridge as well as the substituent at the para position of the phenolic ring.