Transient changes in aromaticity and their effect on excited-state proton transfer reactions. Issue 19 (4th May 2022)

• Record Type: Journal Article
• Authors: Arpa, Enrique M.; Durbeej, Bo
• Is Part Of: Physical chemistry chemical physics. Volume 24:Issue 19(2022)
• Page Start: 11496
• Page End: 11500
• Publication Date: 2022-05-04
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d2cp00494a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Quantum chemical modelling shows that energy barriers for excited-state proton transfer reactions involving 2-pyridone are governed by the transient onset of antiaromaticity upon interaction between the photoexcited state and a second excited state. Abstract : The common approach to investigate the impact of aromaticity on excited-state proton transfer by probing the (anti)aromatic character of reactants and products alone is scrutinized by modelling such reactions involving 2-pyridone. Thereby, it is found that energy barriers can be strongly influenced by transient changes in aromaticity unaccounted for by this approach, particularly when the photoexcited state interacts with a second excited state. Overall, the modelling identifies a pronounced effect overlooked by most studies on this topic.