Synthesis of new macrobicyclic tricompartmental ligands and site preference of metal ion: structural and electrochemical properties of mononuclear copper(II) complexes |
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| Affiliation: | 1. Department of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, Kerala, India;2. Department of Chemistry School of Physical Sciences, Central University of Kerala, Nileshwar 671314, India;1. State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, 430074, China;2. School of Energy and Power Engineering, Huazhong University of Science and Technology, Wuhan, 430074, China;3. School of Mechanical Manufacture and Automation, Huazhong University of Science and Technology, Wuhan, 430074, China;1. Bioinformatics Unit, South African Tuberculosis Bioinformatics Initiative, Division of Molecular Biology and Human Genetics, Department of Biomedical Sciences, Stellenbosch University, Cape Town, South Africa;2. South African Medical Research Council Centre for Tuberculosis Research, Stellenbosch University, Cape Town, South Africa;3. Centre for Bioinformatics and Computational Biology, Stellenbosch University, Stellenbosch, South Africa;4. Institute of Infectious Disease and Molecular Medicine, Department of Integrative Biomedical Sciences, University of Cape Town, Cape Town, South Africa;5. Department of Paediatrics, Red Cross Children’s Hospital, University of Cape Town, Cape Town, South Africa;6. Council for Scientific and Industrial Research, Pretoria, South Africa |
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| Abstract: | New macrobicyclic tricompartmental ligands and their mononuclear copper(II) complexes of type CuH2L](ClO4)2 have been synthesized from the precursor compound 3,4:10,11-dibenzo-1,13N,N′{bis(3-formyl-2-hydroxy-5-methyl)benzyl}diaza]-5,9-dioxa-cycloheptadecane with diamines like en, pn and bn by template method. These complexes have been characterized by IR, UV spectral and X-ray studies. Complex CuH2L3](ClO4)2 (in L3 the diamine used is bn) crystallized as triclinic system with space group p-1. The crystal structure explains that the geometry around copper is distorted square planar. Among the three compartments, it is interesting to observe that the metal ion prefers to be encompassed by the compartment containing phenolic oxygens and imine nitrogens (N2O2). From X-ray studies the presence of perchlorate anions, acetonitrile solvent molecules and the protonation of tertiary nitrogen atoms were well understood. All the complexes show hyperfine splittings in ESR spectra. The μeff values observed in the range 1.69–1.72 BM are close to the spin only value of single copper(II) ion. Cyclic voltammetry studies of these complexes depict one electron quasireversible reduction in the range −0.80 to −0.90 V at negative potential. A red shift in UV–Visible spectra and shifting of reduction potential towards anodic in cyclic voltammetry were witnessing the distortion of the geometry around metal center from the planarity as the macrocyclic chain length in imine nitrogen compartment increases. |
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