Anion binding by catechols—an NMR, optical and electrochemical study

Abstract

The X-ray structure of the ClC chloride channel made it clear that O–H⋯chloride interactions play a key role in important biological membrane-bound systems, however, surprisingly this type of interaction has only been rarely exploited for the development of synthetic anion receptors. This paper therefore reports the anion binding strengths and selectivities of some simple commercially available bis-phenols. In particular, we compare catechol (1,2-dihydroxybenzene) and resorcinol (1,3-dihydroxybenzene) which show interesting and different selectivities between the halide anions in acetonitrile solution. Catechol binds tetrabutylammononium (TBA) chloride almost 30 times more strongly than TBA bromide, whilst for resorcinol, this difference drops to a factor of ca. 3.5. It is suggested that this is a consequence of the bite angle of the chelating hydogen bonding groups of catechol being particularly appropriate for effective binding of the smaller anion. The oxidation of catechol to ortho-quinone is perturbed by the addition of chloride anions, as probed via cyclic voltammetry, and this compound can therefore be considered to act as an electrochemical sensor for chloride. Nitrocatechol is able to bind chloride anions more strongly than catechol as a consequence of its enhanced acidity and hence greater hydrogen bond donor character. Furthermore, nitrocatechol senses the bound anion via changes in its UV-visible spectrum. Notably, binding still occurs even in the presence of small amounts of competitive solvents (e.g. water). This observation has biomimetic importance as wet acetonitrile has some similarity in terms of overall polarity and hydrogen bond competition to the solvent shielded interiors of biological macromolecules and membranes—such as the environment within the ClC chloride channel itself. Finally, we report that catechol undergoes a unique colorimetric response on the addition of basic anions, such as fluoride. We can assign this response as being due to oxidative degradation of catechol catalysed by the basic anions (which bind to, and deprotonate, the catechol). This process is somewhat analogous to the well-known metal catalysed oxidation of catechol which can take place in aqueous solution. The speed of response and easily monitored and distinctive colour change induced by fluoride anions indicates this may be a useful mechanism for exploitation in the development of selective fluoride sensors.