Can Plasmon Change Reaction Path? Decomposition of Unsymmetrical Iodonium Salts as an Organic Probe

Elena Miliutina, Olga Guselnikova, Natalia S. Soldatova, Polina Bainova, Roman Elashnikov, Přemysl Fitl, Theo Kurten, Mekhman S. Yusubov, Václav Švorčík, Rashid R. Valiev, Mohamed M. Chehimi, Oleksiy Lyutakov, Pavel S. Postnikov

Research output: Contribution to journalArticle

Abstract

Plasmon-assisted transformations of organic compounds represent a novel opportunity for conversion of light to chemical energy at room temperature. However, the mechanistic insights of interaction between plasmon energy and organic molecules is still under debate. Herein, we proposed a comprehensive study of the plasmon-assisted reaction mechanism using unsymmetric iodonium salts (ISs) as an organic probe. The experimental and theoretical analysis allow us to exclude the possible thermal effect or hot electron transfer. We found that plasmon interaction with unsymmetrical ISs led to the intramolecular excitation of electron followed by the regioselective cleavage of C-I bond with the formation of electron-rich radical species, which cannot be explained by the hot electron excitation or thermal effects. The high regioselectivity is explained by the direct excitation of electron to LUMO with the formation of a dissociative excited state according to quantum-chemical modeling, which provides novel opportunities for the fine control of reactivity using plasmon energy.

Original languageEnglish
Pages (from-to)5770-5776
Number of pages7
JournalJournal of Physical Chemistry Letters
Volume11
Issue number14
DOIs
Publication statusPublished - 16 Jul 2020

ASJC Scopus subject areas

  • Materials Science(all)
  • Physical and Theoretical Chemistry

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