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    Photoinduced Charge Accumulation and Prolonged Multielectron Storage for the Separation of Light and Dark Reaction
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    • Martin Schulz*
      Martin Schulz
      Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany
      Department Functional Interfaces, Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Str. 9, 07745 Jena, Germany
      *[email protected]
      More by Martin Schulz
      Orcidhttp://orcid.org/0000-0003-4989-5207
    • Nina Hagmeyer
      Nina Hagmeyer
      Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany
      More by Nina Hagmeyer
    • Frerk Wehmeyer
      Frerk Wehmeyer
      Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany
      More by Frerk Wehmeyer
    • Grace Lowe
      Grace Lowe
      Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany
      More by Grace Lowe
    • Marco Rosenkranz
      Marco Rosenkranz
      Leibniz Institute for Solid State and Materials Research, Helmholtzstraße 20, 01069 Dresden, Germany
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    • Bianca Seidler
      Bianca Seidler
      Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany
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    • Alexey Popov
      Alexey Popov
      Leibniz Institute for Solid State and Materials Research, Helmholtzstraße 20, 01069 Dresden, Germany
      More by Alexey Popov
      Orcidhttp://orcid.org/0000-0002-7596-0378
    • Carsten Streb
      Carsten Streb
      Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm, Germany
      More by Carsten Streb
      Orcidhttp://orcid.org/0000-0002-5846-1905
    • Johannes G. Vos
      Johannes G. Vos
      SRC for Solar Energy Conversion, School of Chemical Sciences, Dublin City University, Dublin, Ireland
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    • Benjamin Dietzek
      Benjamin Dietzek
      Institute of Physical Chemistry, Friedrich Schiller University Jena, Helmholtzweg 4, 07743 Jena, Germany
      Department Functional Interfaces, Leibniz Institute of Photonic Technology (IPHT), Albert-Einstein-Str. 9, 07745 Jena, Germany
      Centre for Energy and Environmental Chemistry (CEEC), Friedrich Schiller University Jena, Philosophenweg 7a, 07743 Jena, Germany
      More by Benjamin Dietzek
      Orcidhttp://orcid.org/0000-0002-2842-3537
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 37, 15722–15728
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    https://doi.org/10.1021/jacs.0c03779
    Published August 22, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    The utilization of solar energy is restricted by the intermittent nature of solar influx. We present novel noble-metal free complexes that can be photochemically charged in the presence of sacrificial electron donors and remain stable in its charged form for over 14 h. This allows the doubly reduced Cu(I) 4H-imidazolate complex to be stored after photochemical charging and used as a reagent in dark reactions, such as the reduction of methyl viologen or oxygen. Combined UV–vis/EPR spectroelectrochemistry indicates that a two-electron reduction is induced by introducing sacrificial electron donors that facilitate proton-coupled electron transfer. Repeated photochemical reduction and chemical oxidation reveals that the complex retained a charging capacity of 72% after four cycles. We demonstrate a chemical system that can decouple photochemical processes from the day–night cycle, which has been a barrier to realizing utilization of solar energy in photochemical processes on a global scale.

    Copyright © 2020 American Chemical Society

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    • Detailed synthetic methods and structural characterization data, electrochemistry, UV–vis/EPR-spectroelectrochemistry, and ns-transient absorption data as well as irradiation methods and data (PDF)

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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2020, 142, 37, 15722–15728
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.0c03779
    Published August 22, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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