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    Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2021, 143, 2, 1098–1106
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    https://doi.org/10.1021/jacs.0c11895
    Published December 30, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    We assembled eight cofacial porphyrin prisms using MTPyP (M = Co(II) or Zn(II), TPyP = 4-tetrapyridylporphyrin) and functionalized ruthenium-based “molecular clips” using coordination-driven self-assembly. Our approach allows for the rapid synthesis of these architectures in isolated yields as high as 98% for the assembly step. Structural and reactivity studies provided a deeper understanding of the role of the building blocks on the oxygen reduction reaction (ORR). Catalytic efficacy was probed by using cyclic and hydrodynamic voltammetry on heterogeneous catalyst inks in aqueous media. The reported prisms showed outstanding selectivity (>98%) for the kinetically hindered 4e–/4H+ reduction of O2 to H2O over the kinetically more accessible 2e–/2H+ reduction to H2O2. Furthermore, we have demonstrated significant cofacial enhancement in the observed catalytic rate constant ks (∼5 orders of magnitude) over the mononuclear analogue. We conclude that the steric bulk of the clip plays an important role in the structural dynamics of these prisms, which in turn modulates the ORR reactivity with respect to selectivity and kinetics.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c11895.

    • Synthetic procedure and spectroscopic characterization data (HR-MS, NMR, IR, UV/vis), crystallographic details, electrochemical characterization, and a detailed discussion of catalyst performance (PDF)

    • Crystallographic data of Ru-CF3 (CIF)

    • Crystallographic data of Zn-CF3 (CIF)

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    This article is cited by 45 publications.

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    Cite this: J. Am. Chem. Soc. 2021, 143, 2, 1098–1106
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.0c11895
    Published December 30, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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