Issue 12, 2023

Wavelength dependent mechanism of phenolate photooxidation in aqueous solution

Abstract

Phenolate photooxidation is integral to a range of biological processes, yet the mechanism of electron ejection has been disputed. Here, we combine femtosecond transient absorption spectroscopy, liquid-microjet photoelectron spectroscopy and high-level quantum chemistry calculations to investigate the photooxidation dynamics of aqueous phenolate following excitation at a range of wavelengths, from the onset of the S0–S1 absorption band to the peak of the S0–S2 band. We find that for λ ≥ 266 nm, electron ejection occurs from the S1 state into the continuum associated with the contact pair in which the PhO˙ radical is in its ground electronic state. In contrast, we find that for λ ≤ 257 nm, electron ejection also occurs into continua associated with contact pairs containing electronically excited PhO˙ radicals and that these contact pairs have faster recombination times than those containing PhO˙ radicals in their ground electronic state.

Graphical abstract: Wavelength dependent mechanism of phenolate photooxidation in aqueous solution

Supplementary files

Article information

Article type
Edge Article
Submitted
02 yan 2023
Accepted
19 fev 2023
First published
20 fev 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 license

Chem. Sci., 2023,14, 3257-3264

Wavelength dependent mechanism of phenolate photooxidation in aqueous solution

K. Robertson, W. G. Fortune, J. A. Davies, Anton N. Boichenko, M. S. Scholz, O. Tau, A. V. Bochenkova and H. H. Fielding, Chem. Sci., 2023, 14, 3257 DOI: 10.1039/D3SC00016H

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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