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Keywords:

  • chemoselectivity;
  • plasmon chemistry;
  • radical reactions;
  • Raman spectroscopy;
  • surface chemistry

Abstract

Heterogeneous catalysts play an important role in surface catalytic reactions, but selective bond breaking and control of reaction products in catalytic processes remain significant challenges. High-vacuum tip-enhanced Raman spectroscopy (HV-TERS) is one of the best candidates to realize surface catalytic reactions. Herein, HV-TERS was employed in a new method to control dissociation by using hot electrons, generated from plasmon decay, as plasmonic scissors. In this method, the N[DOUBLE BOND]N bond in 4,4′-dimercaptoazobenzene was selectively dissociated by plasmonic scissors, and the reaction products formed from the radical fragment (SC6H5N) were controlled by varying the pH value. Under acidic conditions, p-aminothiophenol was produced from the radical fragment by attachment of hydrogen ions, whereas under alkaline conditions, 4-nitrobenzenethiol was obtained by attachment of oxygen ions to the substrate.