Issue 7, 2023

Electric fields drive bond homolysis

Abstract

Electric fields have been used to control and direct chemical reactions in biochemistry and enzymatic catalysis, yet directly applying external electric fields to activate reactions in bulk solution and to characterize them ex situ remains a challenge. Here we utilize the scanning tunneling microscope-based break-junction technique to investigate the electric field driven homolytic cleavage of the radical initiator 4-(methylthio)benzoic peroxyanhydride at ambient temperatures in bulk solution, without the use of co-initiators or photochemical activators. Through time-dependent ex situ quantification by high performance liquid chromatography using a UV-vis detector, we find that the electric field catalyzes the reaction. Importantly, we demonstrate that the reaction rate in a field increases linearly with the solvent dielectric constant. Using density functional theory calculations, we show that the applied electric field decreases the dissociation energy of the O–O bond and stabilizes the product relative to the reactant due to their different dipole moments.

Graphical abstract: Electric fields drive bond homolysis

Supplementary files

Article information

Article type
Edge Article
Submitted
21 Nov 2022
Accepted
15 Jan 2023
First published
16 Jan 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 1769-1774

Electric fields drive bond homolysis

B. Zhang, C. Schaack, C. R. Prindle, E. A. Vo, M. Aziz, M. L. Steigerwald, T. C. Berkelbach, C. Nuckolls and L. Venkataraman, Chem. Sci., 2023, 14, 1769 DOI: 10.1039/D2SC06411A

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