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On the Determination of Halogen Atom Reduction Potentials with Photoredox Catalysts

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Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. A 2021, 125, 42, 9355-9367
    A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters

    On the Determination of Halogen Atom Reduction Potentials with Photoredox Catalysts
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    • Alexander M. Deetz
      Alexander M. Deetz
      Department of Chemistry, University of North Carolina at Chapel Hill, Murray Hall 2202B, Chapel Hill, North Carolina 27599-3290, United States
      More by Alexander M. Deetz
    • Ludovic Troian-Gautier
      Ludovic Troian-Gautier
      Department of Chemistry, University of North Carolina at Chapel Hill, Murray Hall 2202B, Chapel Hill, North Carolina 27599-3290, United States
      More by Ludovic Troian-Gautier
      Orcidhttps://orcid.org/0000-0002-7690-1361
    • Sara A. M. Wehlin
      Sara A. M. Wehlin
      Department of Chemistry, University of North Carolina at Chapel Hill, Murray Hall 2202B, Chapel Hill, North Carolina 27599-3290, United States
      More by Sara A. M. Wehlin
    • Eric J. Piechota
      Eric J. Piechota
      Department of Chemistry, University of North Carolina at Chapel Hill, Murray Hall 2202B, Chapel Hill, North Carolina 27599-3290, United States
      More by Eric J. Piechota
      Orcidhttps://orcid.org/0000-0003-0835-5423
    • Gerald J. Meyer*
      Gerald J. Meyer
      Department of Chemistry, University of North Carolina at Chapel Hill, Murray Hall 2202B, Chapel Hill, North Carolina 27599-3290, United States
      *Email: [email protected]
      More by Gerald J. Meyer
      Orcidhttps://orcid.org/0000-0002-4227-6393
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2021, 125, 42, 9355–9367
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    https://doi.org/10.1021/acs.jpca.1c06772
    Published October 19, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    The standard one-electron reduction potentials of halogen atoms, E°′(X•/–), and many other radical or unstable species, are not accessible through standard electrochemical methods. Here, we report the use of two Ir(III) photoredox catalysts to initiate chloride, bromide, and iodide oxidation in organic solvents. The kinetic rate constants were critically analyzed through a derived diffusional model with Marcus theory to estimate E°′(X•/–) in propylene carbonate, acetonitrile, butyronitrile, and dichloromethane. The approximations commonly used to determine diffusional rate constants in water gave rise to serious disagreements with the experiment, particularly in high-ionic-strength dichloromethane solutions, indicating the need to utilize the exact Debye expression. The Fuoss equation was adequate for determining photocatalyst–halide association constants with photocatalysts that possessed +2, +1, and 0 ionic charges. Similarly, the work term contribution in the classical Rehm–Weller expression, necessary for E°′(X•/–) determination, accounted remarkably well for the stabilization of the charged reactants as the solution ionic strength was increased. While a sensitivity analysis indicated that the extracted reduction potentials were all within experimental error the same, use of fixed parameters established for aqueous solution provided the periodic trend expected, E°′(I•/–) <E°′(Br•/–) <E°′(Cl•/–), in all of the organic solvents investigated; however, the potentials were more closely spaced than what would have been predicted based on gas-phase electron affinities or aqueous reduction potentials. The origin(s) of such behavior are discussed that provide new directions for future research.

    Copyright © 2021 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.jpca.1c06772.

    • Electron-transfer rate constants, solvent parameters, time-resolved photoluminescence quenching, Stern–Volmer plots, and transient absorption spectroscopy (PDF)

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    This article is cited by 26 publications.

    1. Matthew J. Goodwin, Alexander M. Deetz, Paul J. Griffin, Gerald J. Meyer. Periodic Trends in Intra-ionic Excited State Quenching by Halide. Inorganic Chemistry 2024, 63 (34) , 15772-15783. https://doi.org/10.1021/acs.inorgchem.4c01726
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    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2021, 125, 42, 9355–9367
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.1c06772
    Published October 19, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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