Issue 38, 2024

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.

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

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Article information

Article type
Edge Article
Submitted
18 7 2024
Accepted
21 8 2024
First published
28 8 2024
This article is Open Access

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

Chem. Sci., 2024,15, 15565-15576

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

B. Dereka, N. Maroli, Y. M. Poronik, D. T. Gryko and A. A. Kananenka, Chem. Sci., 2024, 15, 15565 DOI: 10.1039/D4SC04797D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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