Anchoring H-Bond Donating/Accepting Pyrrolic Derivatives on Preorganized Scaffolds: Conformationally Switchable Bipedal/Tripodal and Locked Molecular Cage Ionophores for Potentiometric Sensing of Phosphate and Fluoride.

Abstract

The ionophore properties of a myriad of conformationally switchable bipedal/tripodal receptors and locked molecular cages were evaluated here for the first time to fabricate potentiometric sensors for the determination of environmentally important phosphate and fluoride. Owing to the competent ionophore properties such as high binding selectivity and affinity, the developed ion-selective electrodes displayed response preference for phosphate and fluoride with a selectivity pattern that differs distinctly from traditional Hofmeister series. Binding constants of the ionophore-anion complexes are determined to underscore how modifications in the preorganization and H-bond donating/accepting ability of a given series of ionophores can be exploited to improve the performance for potentiometric sensing. While conformationally switchable bipedal/tripodal ionophores prefer tetrahedral oxyanions, locked molecular cages shift their preference to spherical halides gradually. Nernstian potential responses with good reversibility to target anions can be observed when shifting the optimized membrane electrodes in aqueous solutions within the concentration range of 10-6.5-10-2.0 M. Moreover, potentiometric determination of phosphate and fluoride in mineral water, soil, and tap water samples was achieved in a low μM concentration range with high accuracy, confirming their promising utility in real world applications.