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.

Chemistry and Nanoscience Center National Renewable Energy Laboratory Golden CO 80401 USA

ChemMatCARS University of Chicago Lemont IL 60439 USA

Department of Chemistry University of Colorado Boulder CO 80309 USA

Department of Physics University of Colorado Boulder CO 80309 USA

Institute of Organic Chemistry and Biochemistry Czech Academy of Sciences Prague Czech Republic

Renewable and Sustainable Energy Institute at the University of Colorado Boulder CO 80303 USA

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Electronic Structure of Metalloporphenes, Antiaromatic Analogues of Graphene