Porphene and porphite as porphyrin analogs of graphene and graphite
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 th...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
| Language: | English |
| Published: |
Nature Portfolio
2023-10-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-023-41461-w |
| _version_ | 1827709533961584640 |
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| author | 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 |
| author_facet | 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 |
| author_sort | Thomas F. Magnera |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-03-10T17:23:18Z |
| format | Article |
| id | doaj.art-4caedcf8b62745c3a6a56983b496911b |
| institution | Directory Open Access Journal |
| issn | 2041-1723 |
| language | English |
| last_indexed | 2024-03-10T17:23:18Z |
| publishDate | 2023-10-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj.art-4caedcf8b62745c3a6a56983b496911b2023-11-20T10:16:16ZengNature PortfolioNature Communications2041-17232023-10-0114111310.1038/s41467-023-41461-wPorphene and porphite as porphyrin analogs of graphene and graphiteThomas F. Magnera0Paul I. Dron1Jared P. Bozzone2Milena Jovanovic3Igor Rončević4Edward Tortorici5Wei Bu6Elisa M. Miller7Charles T. Rogers8Josef Michl9Department of Chemistry, University of ColoradoDepartment of Chemistry, University of ColoradoDepartment of Chemistry, University of ColoradoDepartment of Chemistry, University of ColoradoInstitute of Organic Chemistry and Biochemistry, Czech Academy of SciencesDepartment of Physics, University of ColoradoChemMatCARS, University of ChicagoChemistry and Nanoscience Center, National Renewable Energy LaboratoryDepartment of Physics, University of ColoradoDepartment of Chemistry, University of ColoradoAbstract 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.https://doi.org/10.1038/s41467-023-41461-w |
| spellingShingle | 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 Porphene and porphite as porphyrin analogs of graphene and graphite Nature Communications |
| title | Porphene and porphite as porphyrin analogs of graphene and graphite |
| title_full | Porphene and porphite as porphyrin analogs of graphene and graphite |
| title_fullStr | Porphene and porphite as porphyrin analogs of graphene and graphite |
| title_full_unstemmed | Porphene and porphite as porphyrin analogs of graphene and graphite |
| title_short | Porphene and porphite as porphyrin analogs of graphene and graphite |
| title_sort | porphene and porphite as porphyrin analogs of graphene and graphite |
| url | https://doi.org/10.1038/s41467-023-41461-w |
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