Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction
Résumé
We report the experimental reassessment of the commonly admitted concerted reduction mechanism for the diazonium electroreduction. Ultrafast cyclic voltammetry was exploited to demonstrate the existence of a stepwise pathway and real-time spectroelectrochemistry experiments allowed to visualize the spectral signature of an evolution product of the nitrophenyldiazenyl radical intermediate. Unambiguous identification of the diazenyl species was achieved by radical trapping followed by X-ray structure resolution. This study brings the evidence of our incomplete understanding of the diazonium electroreduction and calls into question our comprehension of the layer structuration when surface modification is achieved via the diazonium electrografting technique. The systematic presence of azo bridges in the nanometric films is likely due to the direct grafting of the aryldiazenyl radical intermediate evidenced here.
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J phys chem Letter 2022.pdf (615.67 Ko)
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Supplementary information j phys chem Letter 2022.pdf (2.36 Mo)
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Origine : Fichiers produits par l'(les) auteur(s)
Licence : CC BY NC SA - Paternité - Pas d'utilisation commerciale - Partage selon les Conditions Initiales
Licence : CC BY NC SA - Paternité - Pas d'utilisation commerciale - Partage selon les Conditions Initiales
Origine : Fichiers produits par l'(les) auteur(s)
Licence : CC BY NC SA - Paternité - Pas d'utilisation commerciale - Partage selon les Conditions Initiales
Licence : CC BY NC SA - Paternité - Pas d'utilisation commerciale - Partage selon les Conditions Initiales
