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

Draženović, Josip; Laconsay, Croix J.; Došlić, Nađa; Wu, Judy I-Chia; Basarić, Nikola (2024) Excited-state antiaromaticity relief drives facile photoprotonation of carbons in aminobiphenyls. Chemical Science, 15 (14). pp. 5225-5237. ISSN 2041-6520

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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.

Item Type:	Article
Uncontrolled Keywords:	ADC(2) computations; Excited-state antiaromaticity; Excited-state intramolecular proton transfer (ESIPT); Nitrogen photoacids; Isotopic labeling; Photoredox chemistry; Water-splitting
Subjects:	NATURAL SCIENCES > Chemistry > Physical Chemistry NATURAL SCIENCES > Chemistry > Theoretical Chemistry NATURAL SCIENCES > Chemistry > Organic Chemistry
Divisions:	Division of Organic Chemistry and Biochemistry Division of Physical Chemistry
Projects:	Project title Project leader Project code Project type Fotoinducirani procesi u molekulama: Susret teorije i eksperimenta-PhInMol Nađa Došlić IP-2022-10-4658 HRZZ Fotokemija: Reakcijski mehanizmi i primjene u organskoj sintezi i biologiji-PhotoApp Nikola Basarić; Irena Škorić; Dragana Vuk IP-2019-04-8008 HRZZ Efekt kvantnog tuneliranja: dinamika molekula s kvantnim jezgrama-QuanTunMol Marko Tomislav Cvitaš IP-2020-02-9932 HRZZ
Depositing User:	Nikola Basarić
Date Deposited:	20 Jan 2026 13:22
URI:	http://fulir.irb.hr/id/eprint/10989
DOI:	10.1039/D4SC00642A

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