Metalloporphenes, a new family of conjugated 2-dimensional polymers

Thomas F. Magnera¹, Paul I. Dron¹, Jared P. Bozzone¹, Milena Jovanović¹, Igor Rončević², Edward Tortorici³, Wei Bu⁴, Elisa M. Miller⁵, Charles T. Rogers³, and Josef Michl^1,2

1 Department of Chemistry, University of Colorado, Boulder, CO 80309, U.S.A.
2 Institute of Organic Chemistry and Biochemistry, CAS; Prague, Czech Republic.
3 Department of Physics, University of Colorado, Boulder, Colorado 80309, U.S.A.
4 ChemMatCARS, University of Chicago; Lemont, IL 60439, U.S.A.
5 Chemistry and Nanoscience Center, NREL; Golden, CO 80401, U.S.A.

Two-dimensional materials have unusual properties and promise applications in nanoelectronics, spintronics, photonics, etc. Most are inorganic and their properties are difficult to tune. We have prepared Zn porphene, a fully conjugated two-dimensional organic polymers composed of fused porphyrin rings, by oxidative polymerization of a Langmuir bilayer of Zn porphyrin on water surface. It is transferable to other substrates and bridges μm-sized pits. Contrary to previous theoretical predictions, it is a p-type semiconductor due to a distortion of its unit cell from square to rectangular shape, analogous to the appearance of bond-length alternation in antiaromatic molecules. Reversible insertion of metal ions, possibly with a fifth or sixth ligand, promises patterning circuits on an atomic canvas without removing any π centers from conjugation.

This talk is for the Therien symposium.