On-surface synthesis of nonbenzenoid PAHs using intermolecular π-radical C-C coupling

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68378271%3A_____%2F25%3A00642925" target="_blank" >RIV/68378271:_____/25:00642925 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989592:15640/25:73632759

Výsledek na webu

<a href="https://hdl.handle.net/11104/0373436" target="_blank" >https://hdl.handle.net/11104/0373436</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/jacs.5c12864" target="_blank" >10.1021/jacs.5c12864</a>

Jazyk výsledku

angličtina

Název v původním jazyce

On-surface synthesis of nonbenzenoid PAHs using intermolecular π-radical C-C coupling

Popis výsledku v původním jazyce

On-surface synthesis has emerged as a new research field, ideal for designing low-dimensional carbon-based nanomaterials. One of the central problems with this synthetic approach is the understanding of reaction mechanisms, which is a key point for advancing the design of novel, highly selective reactions. The concept of π-radical-mediated reactions has been rarely considered in the context of on-surface synthesis so far. Here, we demonstrate that a π-radical-mediated reaction can provide an efficient mechanism of regioselective carbon–carbon coupling. Namely, π-radical coupling enables the dimerization of two π-expanded acenaphthene units, which facilitates the formation of complex nonbenzenoid PAHs. Our work contributes to the understanding of reaction mechanisms at the fundamental level, thus bridging the gap between in-solution radical chemistry and on-surface synthesis. We demonstrate a highly selective reaction in which the crucial C–C coupling step proceeds without direct catalytic involvement of the gold surface. This mechanistic insight suggests that π-radical coupling is a promising strategy that could be potentially expanded to inert surfaces, providing suitable π-radical activation.n

Název v anglickém jazyce

On-surface synthesis of nonbenzenoid PAHs using intermolecular π-radical C-C coupling

Popis výsledku anglicky

On-surface synthesis has emerged as a new research field, ideal for designing low-dimensional carbon-based nanomaterials. One of the central problems with this synthetic approach is the understanding of reaction mechanisms, which is a key point for advancing the design of novel, highly selective reactions. The concept of π-radical-mediated reactions has been rarely considered in the context of on-surface synthesis so far. Here, we demonstrate that a π-radical-mediated reaction can provide an efficient mechanism of regioselective carbon–carbon coupling. Namely, π-radical coupling enables the dimerization of two π-expanded acenaphthene units, which facilitates the formation of complex nonbenzenoid PAHs. Our work contributes to the understanding of reaction mechanisms at the fundamental level, thus bridging the gap between in-solution radical chemistry and on-surface synthesis. We demonstrate a highly selective reaction in which the crucial C–C coupling step proceeds without direct catalytic involvement of the gold surface. This mechanistic insight suggests that π-radical coupling is a promising strategy that could be potentially expanded to inert surfaces, providing suitable π-radical activation.n

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA23-05486S" target="_blank" >GA23-05486S: Syntéza na površích a charaketrizace polyradikálních molekul</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2025

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

147

Číslo periodika v rámci svazku

48

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

44123-44130

Kód UT WoS článku

001618573300001

EID výsledku v databázi Scopus

2-s2.0-105023654623