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Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction

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    Physical Insights into Chemistry, Catalysis, and Interfaces

    Highly Reactive Diazenyl Radical Species Evidenced during Aryldiazonium Electroreduction
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2022, 13, 51, 11866–11871
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    https://doi.org/10.1021/acs.jpclett.2c03089
    Published December 15, 2022
    Copyright © 2022 American Chemical Society
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    Abstract

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    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.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.2c03089.

    • Experimental details for electrode treatment, ultrafast cyclic voltammetry, spectroelectrochemistry, radical scavenging and X-ray diffraction; cyclic voltammetry simulations; spectroelectrochemistry current–time curves; spectroelectrochemistry simulations; DFT calculations and TD-DFT simulated spectra; spectroelectrochemistry control experiments; LDI mass spectra (PDF)

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    Crystallographic data for the compound 2 have been deposited with the Cambridge Crystallographic Data Centre with the deposition number CCDC 2151044. These data can be obtained free of charge from CCDC, www.ccdc.cam.ac.uk.

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    This article is cited by 7 publications.

    1. Julien Billon, Elie Bou Rahhal, Tony Breton, Christelle Gautier. Harnessing Aryldiazonium Salts Reduction for Tailored Bifunctionalized Surface Engineering. Chemistry of Materials 2024, 36 (5) , 2220-2230. https://doi.org/10.1021/acs.chemmater.3c03202
    2. Omar Sadek, Jad Rabah, Salem Ba Sowid, Dimitri Mercier, Philippe Marcus, Clément Chauvier, François Ribot, Louis Fensterbank, Emmanuel Maisonhaute. Tailored functional monolayers made from mesoionic carbenes. Electrochimica Acta 2024, 507 , 145189. https://doi.org/10.1016/j.electacta.2024.145189
    3. Max Taras, Jean-Francois Bergamini, Paula A. Brooksby, Philippe Hapiot, Corinne Lagrost, Yann R. Leroux. Patterned organic layers on gold surfaces prepared by electro-grafting of photolabile-protected aryl diazonium salts. RSC Applied Interfaces 2024, 1 (4) , 734-740. https://doi.org/10.1039/D3LF00208J
    4. Baptiste Maillot, Jean-Frédéric Audibert, Fabien Miomandre, Vitor Brasiliense. Nanometrology based control: taming radical grafting reactions with attoliter precision. Nanoscale 2024, 16 (15) , 7594-7602. https://doi.org/10.1039/D3NR06324K
    5. Quentin Lenne, Zaynab Atyf, Jalal Ghilane. When ionic liquids meet diazonium salts to generate thin layers of modified surfaces. Current Opinion in Electrochemistry 2023, 40 , 101338. https://doi.org/10.1016/j.coelec.2023.101338
    6. Luca Nicchio, Jérôme Médard, Philippe Decorse, Sarra Gam‐Derouich, Alexandre Chevillot‐Biraud, Yun Luo, Claire Mangeney, Avni Berisha, Frédéric Averseng, Maurizio Fagnoni, Stefano Protti, Jean Pinson. Selective N sp2 ‐ and C sp2 ‐ Photografting of Au‐Surface by Aryldiazonium Salts and Arylazo Sulfonates. Chemistry – A European Journal 2023, 29 (42) https://doi.org/10.1002/chem.202301006
    7. Nikolaos Kostopoulos, Viacheslav Shkirskiy, Catherine Combellas, Frédéric Kanoufi, Tony Breton, Jean-Marc Noël. Aryldiazonium reduction mechanism deciphered by scanning electrochemical microscopy through an EC’ process. Electrochimica Acta 2023, 444 , 142028. https://doi.org/10.1016/j.electacta.2023.142028
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2022, 13, 51, 11866–11871
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.2c03089
    Published December 15, 2022
    Copyright © 2022 American Chemical Society
    Request reuse permissions

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