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The Pivotal Role of Hot Carriers in Plasmonic Catalysis of C−N Bond Forming Reaction of Amines
Author(s) -
Swaminathan Swathi,
Rao Vishal Govind,
Bera Jitendra K.,
Chandra Manabendra
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202101639
Subject(s) - chemistry , photochemistry , catalysis , charge carrier , redox , raman spectroscopy , spectroscopy , photocatalysis , surface enhanced raman spectroscopy , reaction intermediate , reaction mechanism , nanoparticle , nanotechnology , materials science , organic chemistry , raman scattering , physics , optoelectronics , quantum mechanics , optics
Abstract Here, we demonstrate the simultaneous utilization of both the hot carriers (electrons and holes) in the photocatalytic transformation of benzylamine to N‐benzylidenebenzylamine and the scope of reaction has also been successfully demonstrated with catalytic oxidation of 4‐methoxybenzylamine. The wavelength‐dependent excitation of AuNP allows us to tune the potential energy of charge carriers relative to the redox potential of the reactants which leads to energetically favorable product formation on the nanoparticle surface. We capture the formation of reaction intermediates and products by using in situ Raman spectroscopy, complemented by NMR spectroscopy and GC‐MS. Based on the experimental substantiations, a plausible reaction mechanism has been proposed.

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