Zinc porphene is a two-dimensional material made of fully fused zinc porphyrins in a tetragonal lattice. It has a fully conjugated π-system, making it similar to graphene. Zinc porphene has recently been synthesized, and a combination of rough conductivity measurements and infrared and Raman spectroscopies all suggested that it is a semiconductor (Magnera, T.F. et al. Porphene and Porphite as Porphyrin Analogs of Graphene and Graphite, Nat. Commun.2023, 14, 6308). This is in contrast with all previous predictions of its electronic structure, which indicated metallic conductivity. We show that the gap-opening in zinc porphene is caused by a Peierls distortion of its unit cell from square to rectangular, thus giving the first account of its electronic structure in agreement with the experiment. Accounting for this distortion requires proper treatment of electron delocalization, which can be done using hybrid functionals with a substantial amount of exact exchange. Such a functional, PBE38, is then applied to predict the properties of many first transition row metalloporphenes, some of which have already been prepared. We find that changing the metal strongly affects the electronic structure of metalloporphenes, resulting in a rich variety of both metallic conductors and semiconductors, which may be of great interest to molecular electronics and spintronics. Properties of these materials are mostly governed by the extent of the Peierls distortion and the number of electrons in their π-system, analogous to changes in aromaticity observed in cyclic conjugated molecules upon oxidation or reduction. These results give an account of how the concept of antiaromaticity can be extended to periodic systems.

Cavendish Laboratory Department of Physics University of Cambridge J J Thomson Avenue Cambridge CB3 0HE U K

Department of Chemistry and Biochemistry University of Colorado Boulder Colorado 80309 0215 United States

Department of Chemistry Faculty of Science University of Zagreb Horvatovac 102A Zagreb 10000 Croatia

Department of Chemistry University of Oxford Chemistry Research Laboratory Oxford OX1 3TA U K

Institute of Organic Chemistry and Biochemistry of the CAS Flemingovo nám 2 Prague 6 16610 Czech Republic

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Rapid flipping between electrolyte and metallic states in ammonia solutions of alkali metals

Global Aromatic Ring Currents in Neutral Porphyrin Nanobelts