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Visible Light Generation of a Microsecond Long-Lived Potent Reducing Agent

  • Zijian Zhao
    Zijian Zhao
    Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 220 Handan Road, Shanghai 200433, PR China
    More by Zijian Zhao
  • Fushuang Niu
    Fushuang Niu
    Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 220 Handan Road, Shanghai 200433, PR China
    More by Fushuang Niu
  • Pengju Li
    Pengju Li
    Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 220 Handan Road, Shanghai 200433, PR China
    More by Pengju Li
  • Hanqi Wang
    Hanqi Wang
    Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 220 Handan Road, Shanghai 200433, PR China
    More by Hanqi Wang
  • Zhenghao Zhang
    Zhenghao Zhang
    Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 220 Handan Road, Shanghai 200433, PR China
  • 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]
  • , and 
  • Ke Hu*
    Ke Hu
    Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, 220 Handan Road, Shanghai 200433, PR China
    *Email: [email protected]
    More by Ke Hu
Cite this: J. Am. Chem. Soc. 2022, 144, 16, 7043–7047
Publication Date (Web):March 10, 2022
https://doi.org/10.1021/jacs.2c00422
Copyright © 2022 American Chemical Society

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    Abstract

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    Photoexcitation of molecular radicals can produce strong reducing agents; however, the limited lifetimes of the doublet excited states preclude many applications. Herein, we propose and demonstrate a general strategy to translate a highly energetic electron from a doublet excited state to a ZrO2 insulator, thereby increasing the lifetime by about 6 orders of magnitude while maintaining a reducing potential less than −2.4 V vs SCE. Specifically, red light excitation of a salicylic acid modified perylene diimide radical anion PDI•– anchored to a ZrO2 insulator yields a ZrO2(e)|PDI charge separated state with an ∼10 μs lifetime in 23% yield. The ZrO2(e)s were shown to drive CO2 → CO reduction with a Re catalyst present in micromolar concentrations. More broadly, this strategy provides new opportunities to reduce important reagents and catalysts at low concentrations through diffusional electron transfer.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.2c00422.

    • Experimental details, additional spectroscopic and electrochemical characterizations, parallel photocatalytic CO2 reduction runs, photocatalytic dehalogenation data, kinetic fitting, and injection yield calculations (PDF)

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    Cited By

    This article is cited by 9 publications.

    1. Zijian Zhao, Jili Li, Wei Yuan, Dajiao Cheng, Suze Ma, Ye-Fei Li, Zhang-Jie Shi, Ke Hu. Nature-Inspired Photocatalytic Azo Bond Cleavage with Red Light. Journal of the American Chemical Society 2024, 146 (2) , 1364-1373. https://doi.org/10.1021/jacs.3c09837
    2. Wen-Jie Kang, Bo Li, Zijian Zhao, Shijie Sun, Changhao Feng, Ke Hu, K. N. Houk, Hao Guo. Generation of Thioxanthone Hydrogen Anion by Double Photoreduction and Uses for Catalytic Photoreductions. ACS Catalysis 2023, 13 (20) , 13588-13596. https://doi.org/10.1021/acscatal.3c03972
    3. Hua Su, Wei Wang. In Situ Optical Imaging-Enabled New Insights into Nanoscale Photofunctional Materials: Visualization, Manipulation, and Beyond. The Journal of Physical Chemistry Letters 2023, 14 (23) , 5410-5425. https://doi.org/10.1021/acs.jpclett.3c00963
    4. Mirjam R. Schreier, Björn Pfund, Debora M. Steffen, Oliver S. Wenger. Photocatalytic Regeneration of a Nicotinamide Adenine Nucleotide Mimic with Water-Soluble Iridium(III) Complexes. Inorganic Chemistry 2023, 62 (20) , 7636-7643. https://doi.org/10.1021/acs.inorgchem.2c03100
    5. Youting Fang, Ting Liu, Longxin Chen, Duobin Chao. Morphology Control of Supramolecular Assembly for Superior CO2 Photoreduction. ACS Catalysis 2023, 13 (3) , 2086-2093. https://doi.org/10.1021/acscatal.2c04845
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    9. Miroslav Kohl, Fouzy Alafid, Marek Bouška, Anna Krejčová, Yash Raycha, Andréa Kalendová, Radim Hrdina, Ladislav Burgert. New Corrosion Inhibitors Based on Perylene Units in Epoxy Ester Resin Coatings. Coatings 2022, 12 (7) , 923. https://doi.org/10.3390/coatings12070923

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