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Electrochemical and Plasmon‐induced Grafting of n‐Dopable π‐Conjugated Oligomers
Author(s) -
Bastide Mathieu,
Frath Denis,
GamDerouich Sarra,
Lacroix JeanChristophe
Publication year - 2021
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.202100563
Subject(s) - electrochemistry , pyrazine , conjugated system , surface plasmon resonance , materials science , monomer , photochemistry , electrode , raman spectroscopy , plasmon , surface modification , colloidal gold , x ray photoelectron spectroscopy , redox , nanoparticle , chemistry , chemical engineering , nanotechnology , polymer , organic chemistry , optoelectronics , physics , engineering , optics , composite material , metallurgy
The functionalization of electrodes by the reduction of diazonium cations generated in situ from 4‐(2,3‐diethylthieno[3,4‐b]pyrazine‐5‐yl)aniline has been investigated. The thienopyrazine unit of this molecule is a precursor of n‐dopable π‐conjugated oligomers. Electrochemical reduction of diazonium cation coats the electrode with organic layers. Raman, IR, and XPS analyses show that their composition corresponds to that of the starting monomer, while AFM scratching measurements indicate thicknesses below 10 nm. The electrochemical responses of various reversible redox couples on the modified electrodes show that the attached layer is insulating in the positive potential range but can be n‐doped at negative potential and switches to a conductive state. Moreover, oligo(4‐(2,3‐diethylthieno[3,4‐b]pyrazine‐5‐yl)phenyl) can be selectively grafted onto gold nanoparticles (AuNPs) by plasmon‐induced diazonium reduction. A 10–20 nm‐thick organic layer is easily grafted onto each gold nanoparticle by visible‐light illumination in a few minutes without any reducing agent or molecular photocatalyst. This result is attributed to the transfer of hot electrons from the excited plasmonic NPs to the diazonium, confirms that localized surface plasmon resonance can induce nanolocalized electrochemical reactions, and contributes to the emerging field of “plasmonic electrochemistry”.