Issue 14, 2024

Excited-state antiaromaticity relief drives facile photoprotonation of carbons in aminobiphenyls

Abstract

A combined computational and experimental study reveals that ortho-, meta- and para-aminobiphenyl isomers undergo distinctly different photochemical reactions involving proton transfer. Deuterium exchange experiments show that the ortho-isomer undergoes a facile photoprotonation at a carbon atom via excited-state intramolecular proton transfer (ESIPT). The meta-isomer undergoes water-assisted excited-state proton transfer (ESPT) and a photoredox reaction via proton-coupled electron transfer (PCET). The para-isomer undergoes a water-assisted ESPT reaction. All three reactions take place in the singlet excited-state, except for the photoredox process of the meta-isomer, which involves a triplet excited-state. Computations illustrate the important role of excited-state antiaromaticity relief in these photoreactions.

Graphical abstract: Excited-state antiaromaticity relief drives facile photoprotonation of carbons in aminobiphenyls

Supplementary files

Article information

Article type
Edge Article
Submitted
27 Jan 2024
Accepted
02 Mar 2024
First published
04 Mar 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, 5225-5237

Excited-state antiaromaticity relief drives facile photoprotonation of carbons in aminobiphenyls

J. Draženović, C. J. Laconsay, N. Došlić, J. I-Chia Wu and N. Basarić, Chem. Sci., 2024, 15, 5225 DOI: 10.1039/D4SC00642A

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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