Synthesis and anion-binding properties of novel redox-active calixarene receptors

A novel synthetic approach towards redox-active calixarene-based receptors is described in which ferrocene fragments were introduced at the lower rim through anion-binding urea or amide connections. These derivatives were prepared in one pot by treating an amine-containing calixarene with ferrocenecarboxylic acid in the presence of diphenylphosphoryl azide and diisopropylethylamine. This method allows a convergent approach to these receptors and is readily adaptable to the introduction of other urea substituents. The anion-binding properties of these artificial receptors have been revealed by NMR spectroscopy and thoroughly investigated by electrochemical methods. We have assessed the importance of the urea-phosphate bonds in the observed electrochemical response by studying receptors in which the ferrocene reporters and binding fragments are closely associated or fully disconnected through a long alkyl chain. The experimental results clearly show the utmost importance of ion-pairing effects in the electrochemical recognition process, which account for most of the transduction signal in organic apolar media. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).