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

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.

Abstract

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.

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