Porphene and porphite as porphyrin analogs of graphene and graphite

0576909 - ÚOCHB 2024 RIV US eng J - Článek v odborném periodiku
Magnera, T. F. - Dron, Paul Ionut - Bozzone, J. P. - Jovanovic, M. - Rončević, Igor - Tortorici, E. - Bu, W. - Miller, E. M. - Rogers, C. T. - Michl, Josef
Porphene and porphite as porphyrin analogs of graphene and graphite.
Nature Communications. Roč. 14, October (2023), č. článku 6308. E-ISSN 2041-1723
Grant CEP: GA ČR(CZ) GX20-03691X
Výzkumná infrastruktura: e-INFRA CZ - 90140
Institucionální podpora: RVO:61388963
Klíčová slova: interface-assisted synthesis * fused zinc porphyrins * Peierls instability
Obor OECD: Organic chemistry
Impakt faktor: 16.6, rok: 2022
Způsob publikování: Open access
https://doi.org/10.1038/s41467-023-41461-w

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.
Trvalý link: https://hdl.handle.net/11104/0346295