Excited-state symmetry breaking is an ultrasensitive tool for probing microscopic electric fields

Abstract
Microscopic electric fields are increasingly found to play a pivotal role in catalysis of enzymatic and chemical reactions. Currently, the vibrational Stark effect is the main experimental method used to measure them. Here, we demonstrate how excited-state symmetry breaking can serve as a much more sensitive tool to assess these fields. Using transient infrared spectroscopy on a quadrupolar probe equipped with nitrile groups we demonstrate both its superior sensitivity and that it does not suffer from the notorious hydrogen-bond induced upshift of the C[triple bond, length as m-dash]N stretch frequency. In combination with conventional ground-state infrared absorption, excited-state symmetry breaking can be used to disentangle even weak specific hydrogen bond interactions from general field effects. We showcase this capability with the example of weak C–H hydrogen bonds in polar aprotic solvents. Additionally, we reveal for the first time symmetry breaking driven not by solvent but by the entropy of the pendant side chains of the chromophore. Our findings not only enhance our understanding of symmetry-breaking charge-transfer phenomena but pave the way toward using them in electric field sensing modality.
Description
This article was originally published in Chemical Science. The version of record is available at: https://doi.org/10.1039/D4SC04797D. © 2024 The Author(s). Published by the Royal Society of Chemistry. This Open Access Article is licensed under a Creative Commons Attribution 3.0 Unported Licence (http://creativecommons.org/licenses/by/3.0/).
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Citation
Dereka, Bogdan, Nikhil Maroli, Yevgen M. Poronik, Daniel T. Gryko, and Alexei A. Kananenka. “Excited-State Symmetry Breaking Is an Ultrasensitive Tool for Probing Microscopic Electric Fields.” Chemical Science 15, no. 38 (2024): 15565–76. https://doi.org/10.1039/D4SC04797D.