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

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. Lett. 2020, 11, 14, 5770-5776
    Physical Insights into Chemistry, Catalysis, and Interfaces

    Can Plasmon Change Reaction Path? Decomposition of Unsymmetrical Iodonium Salts as an Organic Probe
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    • Elena Miliutina
      Elena Miliutina
      Research School of Chemistry & Applied Biomedical Sciences, National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050, Russia
      Institute of Chemical Technology, Technicka 5, Prague 16628, Czech Republic
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    • Olga Guselnikova*
      Olga Guselnikova
      Research School of Chemistry & Applied Biomedical Sciences, National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050, Russia
      Institute of Chemical Technology, Technicka 5, Prague 16628, Czech Republic
      *Email: [email protected]
      More by Olga Guselnikova
    • Natalia S. Soldatova
      Natalia S. Soldatova
      Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab., 7/9, Saint Petersburg, Russian Federation
      More by Natalia S. Soldatova
    • Polina Bainova
      Polina Bainova
      Institute of Chemical Technology, Technicka 5, Prague 16628, Czech Republic
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    • Roman Elashnikov
      Roman Elashnikov
      Institute of Chemical Technology, Technicka 5, Prague 16628, Czech Republic
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    • Přemysl Fitl
      Přemysl Fitl
      Institute of Chemical Technology, Technicka 5, Prague 16628, Czech Republic
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    • Theo Kurten
      Theo Kurten
      Department of Chemistry, University of Helsinki, Helsinki FIN-00014, Finland
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      Orcidhttp://orcid.org/0000-0002-6416-4931
    • Mekhman S. Yusubov
      Mekhman S. Yusubov
      Research School of Chemistry & Applied Biomedical Sciences, National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050, Russia
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    • Václav Švorčík
      Václav Švorčík
      Institute of Chemical Technology, Technicka 5, Prague 16628, Czech Republic
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    • Rashid R. Valiev
      Rashid R. Valiev
      Research School of Chemistry & Applied Biomedical Sciences, National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050, Russia
      Department of Chemistry, University of Helsinki, Helsinki FIN-00014, Finland
      More by Rashid R. Valiev
      Orcidhttp://orcid.org/0000-0002-2088-2608
    • Mohamed M. Chehimi
      Mohamed M. Chehimi
      University Paris-Est Créteil, 61 Avenue du Général de Gaulle, 94000 Créteil, France
      More by Mohamed M. Chehimi
      Orcidhttp://orcid.org/0000-0002-6098-983X
    • Oleksiy Lyutakov
      Oleksiy Lyutakov
      Institute of Chemical Technology, Technicka 5, Prague 16628, Czech Republic
      More by Oleksiy Lyutakov
      Orcidhttp://orcid.org/0000-0001-8781-9796
    • Pavel S. Postnikov*
      Pavel S. Postnikov
      Research School of Chemistry & Applied Biomedical Sciences, National Research Tomsk Polytechnic University, Lenin Avenue 30, Tomsk 634050, Russia
      Institute of Chemical Technology, Technicka 5, Prague 16628, Czech Republic
      *Email: [email protected]
      More by Pavel S. Postnikov
      Orcidhttp://orcid.org/0000-0001-9713-1290
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2020, 11, 14, 5770–5776
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.0c01350
    Published June 30, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    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.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.0c01350.

    • Characterization of pristine gold-coated fiber (Figure S1), control experiment without light (Figure S2), plasmon-induced grafting of ISs 1–5 (Figures S3–S7), assignation of SERS peaks (Table S1), characterization of surface by AFM analysis (Figure S8), control experiment with alternative wavelength (Figure S9), control experiment with thermal-induced grafting of IS-1 (Figure S10), description of the samples preparation and measurement techniques, description of the procedure for obtaining of ISs 1–5 and NMR spectra, calculation details and geometry of ISs 1–5 (S1, S2, D0) and decomposition pathways, thermal decomposition of IS-1, structures and atomic coordinates (PDF)

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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2020, 11, 14, 5770–5776
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.0c01350
    Published June 30, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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