Electronic Structure of Metalloporphenes, Antiaromatic Analogues of Graphene

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

Electronic Structure of Metalloporphenes, Antiaromatic Analogues of Graphene

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Electronic Structure of Metalloporphenes, Antiaromatic Analogues of Graphene

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10401 - Organic chemistry

Projekt

<a href="/cs/project/GX20-03691X" target="_blank" >GX20-03691X: Elektrochemická syntéza porfenu</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Journal of the American Chemical Society

ISSN

0002-7863

e-ISSN

1520-5126

Svazek periodika

146

Číslo periodika v rámci svazku

6

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

3992-4000

Kód UT WoS článku

001160876000001

EID výsledku v databázi Scopus

2-s2.0-85184600234