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Université Angers, CNRS, MOLTECH-Anjou, SFR MATRIX, F-49000 Angers, France.
Published: December 2022
AI Article Synopsis
* Using ultrafast cyclic voltammetry and real-time spectroelectrochemistry, researchers observed and identified a phenyldiazenyl radical intermediate and its evolution product.
* The findings suggest that this intermediate might influence the structuration of layers during surface modifications with diazonium electrografting, potentially explaining the presence of azo bridges in nanometric films.
Article Abstract
We report the experimental reassessment of the widely admitted concerted reduction mechanism for diazonium electroreduction. Ultrafast cyclic voltammetry was exploited to demonstrate the existence of a stepwise pathway, and real-time spectroelectrochemistry experiments allowed visualization of the spectral signature of an evolution product of the phenyldiazenyl radical intermediate. Unambiguous identification of the diazenyl species was achieved by radical trapping followed by X-ray structure resolution. The electrochemical generation of this transient under intermediate energetic conditions calls into question our comprehension of the layer structuration when surface modification is achieved via the diazonium electrografting technique as this azo-containing intermediate could be responsible for the systematic presence of azo bridges in nanometric films.
