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Lowering the Symmetry of Cofacial Porphyrin Prisms for Selective Oxygen Reduction Electrocatalysis

  • Daoyang Zhang
    Daoyang Zhang
    Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States
  • Matthew R. Crawley
    Matthew R. Crawley
    Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States
  • Amanda N. Oldacre
    Amanda N. Oldacre
    Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States
  • Lea J. Kyle
    Lea J. Kyle
    Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States
    More by Lea J. Kyle
  • Samantha N. MacMillan
    Samantha N. MacMillan
    Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States
  • , and 
  • Timothy R. Cook*
    Timothy R. Cook
    Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States
    *Email: [email protected]
Cite this: Inorg. Chem. 2023, 62, 5, 1766–1775
Publication Date (Web):June 14, 2022
https://doi.org/10.1021/acs.inorgchem.2c01109
Copyright © 2022 American Chemical Society

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    Abstract

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    Cofacial porphyrin catalysts for the Oxygen Reduction Reaction (ORR) formed via coordination-driven self-assembly have so far been limited to designs with fourfold symmetry, where four molecular clips bridge two porphyrin sites. We have synthesized six PynPhm (Py = pyridyl, Ph = phenyl) metalloporphyrin prisms (Co2+, Zn2+) bridged by molecular clips containing two Rh3+ centers. Four of these structures are lower symmetry, with the Py3Ph and Py2Ph2 prisms containing three and two molecular clips, respectively. The Co2+ species were evaluated for their ORR activity. Cyclic and hydrodynamic voltammetry studies of heterogeneous catalyst inks in aqueous media revealed marked differences in selectivity from ∼5% (Py3Ph) to ∼37% (Py2Ph2) for the formation of H2O2. The single-crystal X-ray structure of the Zn2 Py2Ph2 prism shows an offset between the porphyrin faces. This structural feature may be responsible for the change in selectivity, consistent with previous studies of covalently tethered cofacial porphyrins that have shown that geometry is a critical determinant of two-electron/two-proton versus four-electron/four-proton pathways. Extraction of standard rate constants ks for the ORR revealed a cofacial enhancement of ∼2 orders of magnitude over mononuclear Co2+ tetrapyridyl porphyrin. Even though all the prisms described here use the same molecular clip, the resultant structures, and thus the reactivity for the ORR, differ significantly based on the number and orientation of pyridyl donor groups on the porphyrins, highlighting how coordination-driven self-assembly can be used to rapidly tune dinuclear catalysts.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.2c01109.

    • 1H NMR and DOSY NMR, ESI-MS, cyclic voltammograms, LSV, RDE, and crystallography data tables (PDF)

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    CCDC 2161516 and 2161548 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

    This article is cited by 2 publications.

    1. Matthew R. Crawley, Daoyang Zhang, Timothy R. Cook. Electrocatalytic production of hydrogen peroxide enabled by post-synthetic modification of a self-assembled porphyrin cube. Inorganic Chemistry Frontiers 2022, 10 (1) , 316-324. https://doi.org/10.1039/D2QI02050E
    2. Daoyang Zhang, Matthew R. Crawley, Ming Fang, Lea J. Kyle, Timothy R. Cook. The rigidity of self-assembled cofacial porphyrins influences selectivity and kinetics of oxygen reduction electrocatalysis. Dalton Transactions 2022, 51 (48) , 18373-18377. https://doi.org/10.1039/D2DT02724K

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