Redox-Switchable Chalcogen Bonding for Anion Recognition and Sensing

J Am Chem Soc. 2022 May 18;144(19):8827-8836. doi: 10.1021/jacs.2c02924. Epub 2022 May 6.

Abstract

Inspired by the success of its related sigma-hole congener halogen bonding (XB), chalcogen bonding (ChB) is emerging as a powerful noncovalent interaction with a plethora of applications in supramolecular chemistry and beyond. Despite its increasing importance, the judicious modulation of ChB donor strength remains a formidable challenge. Herein, we present, for the first time, the reversible and large-scale modulation of ChB potency by electrochemical redox control. This is exemplified by both the switching-ON of anion recognition via ChB oxidative activation of a novel bis(ferrocenyltellurotriazole) anion host and switching-OFF reductive ChB deactivation of anion binding potency with a telluroviologen receptor. The direct linking of the redox-active center and ChB receptor donor sites enables strong coupling, which is reflected by up to a remarkable 3 orders of magnitude modulation of anion binding strength. This is demonstrated through large voltammetric perturbations of the respective receptor ferrocene and viologen redox couples, enabling, for the first time, ChB-mediated electrochemical anion sensing. The sensors not only display significant anion-binding-induced electrochemical responses in competitive aqueous-organic solvent systems but can compete with, or even outperform similar, highly potent XB and HB sensors. These observations serve to highlight a unique (redox) tunability of ChB and pave the way for further exploration of the reversible (redox) modulation of ChB in a wide range of applications, including anion sensors as well as molecular switches and machines.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Anions / chemistry
  • Chalcogens*
  • Halogens* / chemistry
  • Oxidation-Reduction
  • Solvents

Substances

  • Anions
  • Chalcogens
  • Halogens
  • Solvents