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Photodetachment photoelectron spectroscopy shows isomer-specific proton-coupled electron transfer reactions in phenolic nitrate complexes.
- Source :
-
Communications chemistry [Commun Chem] 2024 Aug 09; Vol. 7 (1), pp. 176. Date of Electronic Publication: 2024 Aug 09. - Publication Year :
- 2024
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Abstract
- The oxidation of phenolic compounds is one of the most important reactions prevalent in various biological processes, often explicitly coupled with proton transfers (PTs). Quantitative descriptions and molecular-level understanding of these proton-coupled electron transfer (PCET) reactions have been challenging. This work reports a direct observation of PCET in photodetachment (PD) photoelectron spectroscopy (PES) of hydrogen-bonded phenolic (ArOH) nitrate (NO <subscript>3</subscript> <superscript>-</superscript> ) complexes, in which a much slower rising edge provides a spectroscopic signature to evidence PCET. Electronic structure calculations unveil the PCET processes to be isomer-specific, occurred only in those with their HOMOs localized on ArOH, leading to charge-separated transient states ArOH <superscript>•+</superscript> ·NO <subscript>3</subscript> <superscript>-</superscript> triggered by ionizing phenols while simultaneously promoting PT from ArOH <superscript>•+</superscript> to NO <subscript>3</subscript> <superscript>-</superscript> . Importantly, this study showcases that gas-phase PD-PES is a generic means enabling to identify PCET reactions with explicit structural and binding information.<br /> (© 2024. The Author(s).)
Details
- Language :
- English
- ISSN :
- 2399-3669
- Volume :
- 7
- Issue :
- 1
- Database :
- MEDLINE
- Journal :
- Communications chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 39122780
- Full Text :
- https://doi.org/10.1038/s42004-024-01257-5