Electronic Structure Changes of an Aromatic Amine Photoacid along the Förster Cycle.
Aromaticity
Electronic Structure
Orbital Interactions
Photoacids
Time-Resolved Soft x-Ray Spectroscopy
Journal
Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543
Informations de publication
Date de publication:
04 07 2022
04 07 2022
Historique:
received:
14
01
2022
pubmed:
25
3
2022
medline:
30
6
2022
entrez:
24
3
2022
Statut:
ppublish
Résumé
Photoacids show a strong increase in acidity in the first electronic excited state, enabling real-time studies of proton transfer in acid-base reactions, proton transport in energy storage devices and biomolecular sensor protein systems. Several explanations have been proposed for what determines photoacidity, ranging from variations in solvation free energy to changes in electronic structure occurring along the four stages of the Förster cycle. Here we use picosecond nitrogen K-edge spectroscopy to monitor the electronic structure changes of the proton donating group in a protonated aromatic amine photoacid in solution upon photoexcitation and subsequent proton transfer dynamics. Probing core-to-valence transitions locally at the amine functional group and with orbital specificity, we clearly reveal pronounced electronic structure, dipole moment and energetic changes on the conjugate photobase side. This result paves the way for a detailed electronic structural characterization of the photoacidity phenomenon.
Identifiants
pubmed: 35325500
doi: 10.1002/anie.202200709
pmc: PMC9322478
doi:
Substances chimiques
Acids
0
Amines
0
Protons
0
Types de publication
Journal Article
Research Support, Non-U.S. Gov't
Langues
eng
Sous-ensembles de citation
IM
Pagination
e202200709Informations de copyright
© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.
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