Electrochemically driven reversible solid state metal exchange processes in polynuclear copper complexes |
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Authors: | Frank Marken Sarah Cromie Vickie McKee |
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Institution: | (1) Department of Chemistry, Loughborough University, Loughborough, LE11 3TU, UK, |
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Abstract: | The electrochemical characteristics of polynuclear di-copper and tetra-copper complexes of an expanded "Robson-type" macrocyclic
ligand are explored by solid state voltammetry in aqueous media. When adhered to a graphite electrode surface in the form
of microcrystalline powders and immersed in aqueous buffer solution, these water-insoluble polynuclear copper complexes show
well-defined voltammetric reduction and re-oxidation responses. The di-copper metal complexes Cu2(H3L)(OH)]BF4]2 and the tetra-copper complexes Cu4(L)(OH)]NO3]3 with an O4N4 octadentate macrocyclic ligand L are shown to exhibit inter-related and proton concentration sensitive solid state voltammetric
characteristics. At sufficiently negative potential, copper is extracted from the complexes to form a solid copper deposit
and the neutral form of the insoluble free ligand. Upon re-oxidation of the copper deposit, Cu2+ undergoes facile re-insertion into the ligand sphere to re-form solid di- and tetra-copper complexes at the electrode surface.
The reduction process occurs in two stages, with two Cu2+ cations being extracted in each step. The ability of the macrocyclic ligand to efficiently release and accumulate copper
is demonstrated.
Electronic Publication |
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Keywords: | Voltammetry Copper Macrocyclic ligand Electro-insertion Metal extraction |
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