Anti-Hofmeister Anion Selectivity Via a Mechanical Bond Effect in Neutral Halogen-Bonding [2]Rotaxanes

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2022 Oct 20

PMID 36264711

Authors

Andrew Docker

Yuen Cheong Tse

Hui Min Tay

Andrew J Taylor

Zongyao Zhang

Paul D Beer

Affiliations

Soon will be listed here.

Abstract

Exceptionally strong halogen bonding (XB) donor-chloride interactions are exploited for the chloride anion template synthesis of neutral XB [2]rotaxane host systems which contain perfluoroaryl-functionalised axle components, including a remarkably potent novel 4,6-dinitro-1,3-bis-iodotriazole motif. Halide anion recognition properties in aqueous-organic media, determined via extensive H NMR halide anion titration experiments, reveal the rotaxane host systems exhibit dramatically enhanced affinities for hydrophilic Cl and Br , but conversely diminished affinities for hydrophobic I , relative to their non-interlocked axle counterparts. Crucially, this mechanical bond effect induces a binding selectivity which directly opposes Hofmeister bias. Free-energy analysis of this mechanical bond enhancement demonstrates anion recognition by neutral XB interlocked host systems as a rare and general strategy to engineer anti-Hofmeister bias anion selectivity in synthetic receptor design.

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