The role of structural flexibility in plasmon-driven coupling reactions : kinetic limitations in the dimerization of nitro-benzenes
| Autor: | Joachim Koetz, Robin Schürmann, Alexandar R. Milosavljevic, Tina Gaebel, Sergio Kogikoski, Amr Mostafa, Peter Saalfrank, Ferenc Liebig, Evgenii Titov, Wouter Koopman, Clemens N. Z. Schmitt, Ilko Bald, Felix Stete, Radwan M. Sarhan, Matias Bargheer |
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| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Materials science
Mechanical Engineering plasmon driven dimerization bimolecular photoreactions dimerization 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology Photochemistry Rate-determining step 01 natural sciences Coupling reaction 0104 chemical sciences Chemical kinetics Electron transfer chemistry.chemical_compound chemistry Mechanics of Materials Yield (chemistry) Molecule Density functional theory Methylene 0210 nano-technology |
| Zdroj: | Advanced Materials Interfaces |
| Popis: | The plasmon-driven dimerization of 4-nitrothiophenol (4NTP) to 4-4’-dimercaptoazobenzene (DMAB) has become 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, we add structural flexibility 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 towards dimerization. X-ray photoelectron spectroscopy and density functional theory calculations show that the electron transfer would prefer activation of 4NTP over 4NBM. We conclude 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. |
| Databáze: | OpenAIRE |
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