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Porphene and porphite as porphyrin analogs of graphene and graphite

Author

Listed:
  • Thomas F. Magnera

    (University of Colorado)

  • Paul I. Dron

    (University of Colorado
    Czech Academy of Sciences)

  • Jared P. Bozzone

    (University of Colorado)

  • Milena Jovanovic

    (University of Colorado)

  • Igor Rončević

    (Czech Academy of Sciences)

  • Edward Tortorici

    (University of Colorado)

  • Wei Bu

    (University of Chicago)

  • Elisa M. Miller

    (National Renewable Energy Laboratory)

  • Charles T. Rogers

    (University of Colorado
    Renewable and Sustainable Energy Institute (RASEI) at the University of Colorado)

  • Josef Michl

    (University of Colorado
    Czech Academy of Sciences)

Abstract

Two-dimensional materials have unusual properties and promise applications in nanoelectronics, spintronics, photonics, (electro)catalysis, separations, and elsewhere. Most are inorganic and their properties are difficult to tune. Here we report the preparation of Zn porphene, a member of the previously only hypothetical organic metalloporphene family. Similar to graphene, these also are fully conjugated two-dimensional polymers, but are composed of fused metalloporphyrin rings. Zn porphene is synthesized on water surface by two-dimensional oxidative polymerization of a Langmuir layer of Zn porphyrin with K2IrCl6, reminiscent of known one-dimensional polymerization of pyrroles. It is transferable to other substrates and bridges μm-sized pits. Contrary to previous theoretical predictions of metallic conductivity, it is a p-type semiconductor due to a predicted Peierls distortion of its unit cell from square to rectangular, analogous to the appearance of bond-length alternation in antiaromatic molecules. The observed reversible insertion of various metal ions, possibly carrying a fifth or sixth ligand, promises tunability and even patterning of circuits on an atomic canvas without removing any π centers from conjugation.

Suggested Citation

  • Thomas F. Magnera & Paul I. Dron & Jared P. Bozzone & Milena Jovanovic & Igor Rončević & Edward Tortorici & Wei Bu & Elisa M. Miller & Charles T. Rogers & Josef Michl, 2023. "Porphene and porphite as porphyrin analogs of graphene and graphite," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
  • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-41461-w
    DOI: 10.1038/s41467-023-41461-w
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    References listed on IDEAS

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    1. Zhen Zhang & Preeti Bhauriyal & Hafeesudeen Sahabudeen & Zhiyong Wang & Xiaohui Liu & Mike Hambsch & Stefan C. B. Mannsfeld & Renhao Dong & Thomas Heine & Xinliang Feng, 2022. "Cation-selective two-dimensional polyimine membranes for high-performance osmotic energy conversion," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    2. Hafeesudeen Sahabudeen & Haoyuan Qi & Bernhard Alexander Glatz & Diana Tranca & Renhao Dong & Yang Hou & Tao Zhang & Christian Kuttner & Tibor Lehnert & Gotthard Seifert & Ute Kaiser & Andreas Fery & , 2016. "Wafer-sized multifunctional polyimine-based two-dimensional conjugated polymers with high mechanical stiffness," Nature Communications, Nature, vol. 7(1), pages 1-8, December.
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