Inorganic Chemistry

Engineered Binding Microenvironments in Halogen Bonding Polymers for Enhanced Anion Sensing

Authors

Abstract

Mimicking nature’s biopolymeric protein architectures by designing hosts with binding cavities shielded from the bulk solvent environment is a promising approach to achieving anion recognition in competitive protic media. Accomplishing this, however, can be synthetically demanding. Herein we present a more synthetically tractable approach, by directly incorporating potent supramolecular anion recognition motifs into a polymeric scaffold, which can be engineered through a judicious selection of the co-monomer. This is demonstrated through a comprehensive analysis of anion recognition and sensing with redox-active, halogen bonding (XB) polymeric host systems. Notably, the polymeric hosts consistently outperform their monomeric analogues, with especially large halide anion binding enhancements by up to 50-fold observed in aqueous-organic solvent mixtures. These enhancements are rationalised by a consideration of generated low dielectric constant binding microenvironments from which there is appreciable solvent exclusion. This approach is applicable to a range of hosts and targets, enabling recognition and sensing in highly polar media, otherwise unattainable with the monomeric units alone.

Content

Thumbnail image of Manuscript Submitted Nov 9th chemRxiv 14 Nov.pdf

Supplementary material

Thumbnail image of Supporting Information Final High Res.pdf
Engineered Binding Microenvironments in Halogen Bonding Polymers for Enhanced Anion Sensing
Supporting Information