Ditopic redox-active polyferrocenyl zinc(II) dithiocarbamate macrocyclic receptors: synthesis, coordination and electrochemical recognition properties

Wong, W.W.H., Curiel, D., Lai, S.W., Drew, M.G.B. and Beer, P.D. (2005) Ditopic redox-active polyferrocenyl zinc(II) dithiocarbamate macrocyclic receptors: synthesis, coordination and electrochemical recognition properties. Dalton Transactions (4). pp. 774-781. ISSN 1364-5447 doi: 10.1039/b416851h

Abstract/Summary

The synthesis of a range of ditopic polyferrocenyl zinc(II) dithiocarbamate macrocyclic receptors containing ferrocene groups on the macrocycle's periphery and/or as part of the cyclic cavity is reported. The assemblies have been characterised by a range of spectroscopic techniques, electrochemical studies and in two cases by X-ray structure determination. The ability of these host systems to bind and sense electrochemically anionic guest species, isonicotinate and benzoate, and neutral 4-picoline guest was examined by H-1 NMR and cyclic voltammetric titration studies. The strongest association was found between the isonicotinate anion and a dinuclear zinc(II) receptor whose macrocyclic cavity is of complementary size to complex this bidentate guest species in a cooperative manner. Cyclic voltammetric studies demonstrated that all receptors can electrochemically sense the binding of isonicotinate and benzoate via significant cathodic perturbations of the respective ferrocene redox couple.