Electrode‐Potential‐Driven Dissociation of N‐Heterocycle/BF3 Adducts: A Possible Manifestation of the Electro‐Inductive Effect

Recently, non‐Faradaic effects were used to modify the electronic structure and reactivity of electrode‐bound species. We hypothesize that these electrostatic perturbations could influence the chemical reactivity of electrolyte species near an electrode in the absence of Faradaic electron transfer....

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Published inAngewandte Chemie International Edition Vol. 62; no. 24; pp. e202304218 - n/a
Main Authors Hossain, Md. Sazzad, Romo, Adolfo I. B., Putnam, Seth T., Dawlaty, Jahan, Augustyn, Veronica, Rodríguez‐López, Joaquín
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 12.06.2023
EditionInternational ed. in English
Subjects
Adduct
Adducts
Chemical reactions
Electro-Inductive Effect
Electrochemistry
Electrode polarization
Electrodes
Electron transfer
Electronic structure
Electrostatic properties
Electrostatics
Fluorescence
Fluorescence spectroscopy
Perturbation
Redox potential
Scanning Electrochemical Microscopy
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Summary:Recently, non‐Faradaic effects were used to modify the electronic structure and reactivity of electrode‐bound species. We hypothesize that these electrostatic perturbations could influence the chemical reactivity of electrolyte species near an electrode in the absence of Faradaic electron transfer. A prime example of non‐Faradaic effects is acid‐base dissociation near an interface. Here, we probed the near‐electrode dissociation of N‐heterocycle‐BF3 Lewis adducts upon electrode polarization, well outside of the redox potential window of the adducts. Using scanning electrochemical microscopy and confocal fluorescence spectroscopy, we detected a potential‐dependent depletion of the adduct near the electrode. We propose an electro‐inductive effect where a more positive potential leads to electron withdrawal on the N‐heterocycle. This study takes a step forward in the use of electrostatics at electrochemical interfaces for field‐driven electrocatalytic and electro‐synthetic processes. In a non‐redox fashion, applied potential dissociates acid‐base N‐heterocycle‐BF3 couples in the diffusion layer near an electrode. This effect was probed using scanning electrochemical microscopy and confocal fluorescence spectroscopy.
Bibliography:These authors contributed equally to this work.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202304218