Engineered Binding Microenvironments in Halogen Bonding Polymers for Enhanced Anion Sensing

Mimicking Nature's polymeric protein architectures by designing hosts with binding cavities screened from bulk solvent is a promising approach to achieving anion recognition in competitive media. Accomplishing this, however, can be synthetically demanding. Herein we present a synthetically tractable approach, by directly incorporating potent supramolecular anion-receptive motifs into a polymeric scaffold, tuneable through a judicious selection of the co-monomer. A comprehensive analysis of anion recognition and sensing is demonstrated with redox-active, halogen bonding polymeric hosts. Notably, the polymeric hosts consistently outperform their monomeric analogues, with especially large halide binding enhancements of ca. 50-fold observed in aqueous-organic solvent mixtures. These binding enhancements are rationalised by the generation and presentation of low dielectric constant binding microenvironments from which there is appreciable solvent exclusion.

Automated summary

Mimicking Nature's polymeric protein architectures, designing hosts with binding cavities screened from bulk solvent is a promising approach to achieving anion recognition in competitive media. The authors present a synthetically tractable approach by directly incorporating potent supramolecular anion-receptive motifs into a polymeric scaffold. The polymeric hosts consistently outperform their monomeric analogues, with large halide binding enhancements observed in aqueous-organic solvent mixtures.