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  The role of structural flexibility in plasmon-driven coupling reactions : kinetic limitations in the dimerization of nitro-benzenes

Koopman, W., Titov, E., Sarhan, R. M., Gaebel, T., Schürmann, R., Mostafa, A., et al. (2021). The role of structural flexibility in plasmon-driven coupling reactions: kinetic limitations in the dimerization of nitro-benzenes. Advanced Materials Interfaces, 8(22): 2101344. doi:10.1002/admi.202101344.

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 Creators:
Koopman, Wouter, Author
Titov, Evgenii, Author
Sarhan, Radwan M., Author
Gaebel, Tina, Author
Schürmann, Robin, Author
Mostafa, Amr, Author
Kogikoski Jr., Sergio, Author
Milosavljević, Alexandar R., Author
Stete, Felix, Author
Liebig, Ferenc, Author
Schmitt, Clemens N. Z.1, Author              
Koetz, Joachim, Author
Bald, Ilko, Author
Saalfrank, Peter, Author
Bargheer, Matias, Author
Affiliations:
1Luca Bertinetti, Biomaterialien, Max Planck Institute of Colloids and Interfaces, Max Planck Society, ou_2379691              

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Free keywords: coupling reactions, density functional theory calculations, nansocale heat, plasmons, surface-enhanced Raman spectroscopy
 Abstract: Abstract The plasmon-driven dimerization of 4-nitrothiophenol (4NTP) to 4-4′-dimercaptoazobenzene (DMAB) is a testbed for understanding bimolecular photoreactions enhanced by nanoscale metals, in particular, regarding the relevance of electron transfer and heat transfer from the metal to the molecule. By adding a methylene group between the thiol bond and the nitrophenyl, structural flexibility is added to the reactant molecule. Time-resolved surface-enhanced Raman-spectroscopy proves that this (4-nitrobenzyl)mercaptan (4NBM) molecule has a larger dimerization rate and dimerization yield than 4NTP and higher selectivity toward dimerization. X-ray photoelectron spectroscopy and density functional theory calculations show that the electron transfer prefers activation of 4NTP over 4NBM. It is concluded that the rate limiting step of this plasmonic reaction is the dimerization step, which is dramatically enhanced by the additional flexibility of the reactant. This study may serve as an example for using nanoscale metals to simultaneously provide charge carriers for bond activation and localized heat for driving bimolecular reaction steps. The molecular structure of reactants can be tuned to control the reaction kinetics.

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Language(s): eng - English
 Dates: 2021-10-242021
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Type: -
 Identifiers: DOI: 10.1002/admi.202101344
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Title: Advanced Materials Interfaces
  Abbreviation : Adv. Mater. Interfaces
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 8 (22) Sequence Number: 2101344 Start / End Page: - Identifier: ISSN: 2196-7350