Abstract
CH-hydrogen bonding provides access to new building blocks for making macrocyclic ionophores with high degrees of preorganization and selective anion recognition. In this study, an anion-binding ionophore in the shape of a clamshell (ClS) was employed that is composed of two cyanostar (CNstar) macrocycles with preorganized cavities linked with a 12-carbon chain. This ionophore allows for anion complexation by CH-hydrogen bonding. The potentiometric performance of membrane-based ion-selective electrodes incorporating this ionophore was evaluated. Different membrane compositions were prepared to determine the optimum concentrations of the ionophore and lipophilic additive in the membrane. The optimized electrode had a slope of −58.2 mV/decade and demonstrated an anti-Hofmeister selectivity pattern toward iodide with a nanomolar detection limit. Electrospray ionization mass spectrometry was employed to study the relative association strengths of ClS with various anions. The observed mass peaks of the ion–ionophore complexes were found to be consistent with the potentiometric selectivity pattern of the corresponding electrodes. Overall, the selectivity of the electrode could be altered by using an ionophore in which the two CNstar macrocycles are linked together with a flexible 12-carbon chain to control the molecularity of the binding event.
