Synthesis and characterization of new unsymmetrical 'side-off' tetra and hexa coordinate homobinuclear Cu(II) and heterobinuclear Cu(II)-Zn(II) complexes: Magnetic, electrochemical and kinetic studies

Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy
K Shanmuga BharathiV Narayanan

Abstract

A new class of phenol based unsymmetrical side-off tetra and hexa coordinate homobinuclear Cu(II) and heterobinuclear Cu(II)-Zn(II) complexes have been synthesized and characterized by elemental and spectral analysis. The electronic spectra of all the complexes show "Red shift" in LMCT band, for the ligand H(2)L(2) compared to that of the ligand H(2)L(1) due to the relatively higher electron donating nature of their substitutents. The homobinuclear Cu(II) complexes (1 and 2) illustrate an antiferromagnetic interaction (μ(eff): 1.58 and 1.60BM) at 298K with a broad EPR signal. Variable temperature magnetic moment study of the binuclear copper (II) complexes shows that the extent of antiferromagnetic coupling is greater in the case of H(2)L(2) complexes than H(2)L(1) complexes (-2J values: 192cm(-1) and 184cm(-1) respectively). The heterobinuclear Cu(II)-Zn(II) complexes (3 and 4) have a magnetic moment value close to the spin only value with four hyperfine EPR signals. Electrochemical studies of the complexes reveal that all the binuclear complexes show two irreversible one-electron transfer reduction waves in the cathodic region. There is an "anodic shift" in the first reduction potential of the complexes, of the ligand H(2)L(1...Continue Reading

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