期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 144, 期 19, 页码 8827-8836出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c02924
关键词
-
资金
- EPSRC [EP/N509711/1]
- Somerville College, University of Oxford
This study demonstrates for the first time the reversible and large-scale modulation of chalcogen bonding (ChB) potency through electrochemical redox control. By linking the redox-active center and ChB receptor donor sites, the strength of ChB can be effectively regulated, resulting in significant anion binding responses in competitive aqueous-organic solvent systems. The findings highlight the unique tunability of ChB and open up possibilities for further exploration in various applications, including anion sensors, molecular switches, and machines.
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.
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