Photodetachment photoelectron spectroscopy shows isomer-specific proton-coupled electron transfer reactions in phenolic nitrate complexes.
Commun Chem
; 7(1): 176, 2024 Aug 09.
Article
in En
| MEDLINE
| ID: mdl-39122780
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 (NO3-) 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 ArOHâ¢+·NO3- triggered by ionizing phenols while simultaneously promoting PT from ArOHâ¢+ to NO3-. Importantly, this study showcases that gas-phase PD-PES is a generic means enabling to identify PCET reactions with explicit structural and binding information.
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01-internacional
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MEDLINE
Language:
En
Journal:
Commun Chem
Year:
2024
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Article
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