Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction - Sorbonne Université Access content directly
Journal Articles Journal of Physical Chemistry Letters Year : 2022

Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction

Laure Pichereau
  • Function : relator_co_first_author
Thomas Cauchy
Magali Allain
Christelle Gautier
Tony Breton

Abstract

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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Origin : Files produced by the author(s)
Licence : CC BY NC SA - Attribution - NonCommercial - ShareAlike
Origin : Files produced by the author(s)
Licence : CC BY NC SA - Attribution - NonCommercial - ShareAlike

Dates and versions

hal-04303155 , version 1 (13-11-2023)
hal-04303155 , version 2 (23-11-2023)

Licence

Attribution - NonCommercial - ShareAlike

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Laure Pichereau, Laure Fillaud, Nikolaos Kostopoulos, Emmanuel Maisonhaute, Thomas Cauchy, et al.. Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction. Journal of Physical Chemistry Letters, 2022, 13 (51), pp.11866-11871. ⟨10.1021/acs.jpclett.2c03089⟩. ⟨hal-04303155v2⟩
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