Electronic Structure of Metalloporphenes, Antiaromatic Analogues of Graphene

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00582997" target="_blank" >RIV/61388963:_____/24:00582997 - isvavai.cz</a>

Result on the web

<a href="https://doi.org/10.1021/jacs.3c12079" target="_blank" >https://doi.org/10.1021/jacs.3c12079</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.3c12079" target="_blank" >10.1021/jacs.3c12079</a>

Result language

angličtina

Original language name

Electronic Structure of Metalloporphenes, Antiaromatic Analogues of Graphene

Original language description

Zinc porphene is a two-dimensional material made of fully fused zinc porphyrins in a tetragonal lattice. It has a fully conjugated pi-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 pi-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.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10401 - Organic chemistry

Project

<a href="/en/project/GX20-03691X" target="_blank" >GX20-03691X: Electrochemical Synthesis of Porphene</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2024

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

1520-5126

Volume of the periodical

146

Issue of the periodical within the volume

6

Country of publishing house

US - UNITED STATES

Number of pages

9

Pages from-to

3992-4000

UT code for WoS article

001160876000001

EID of the result in the Scopus database

2-s2.0-85184600234