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

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 rea...

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Hauptverfasser: Frezza, Federico (VerfasserIn) , Misselwitz, Erik (VerfasserIn) , Chen, Qifan (VerfasserIn) , Mutombo, Pingo (VerfasserIn) , Rominger, Frank (VerfasserIn) , Sánchez-Grande, Ana (VerfasserIn) , Kivala, Milan (VerfasserIn) , Jelínek, Pavel (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: November 19, 2025
In: Journal of the American Chemical Society
Year: 2025, Jahrgang: 147, Heft: 48, Pages: 44123-44130
ISSN:1520-5126
DOI:10.1021/jacs.5c12864
Online-Zugang:Verlag, kostenfrei, Volltext: https://doi.org/10.1021/jacs.5c12864
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Verfasserangaben:Federico Frezza, Erik Misselwitz, Qifan Chen, Pingo Mutombo, Frank Rominger, Ana Sánchez-Grande, Milan Kivala, and Pavel Jelínek
Beschreibung
Zusammenfassung: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.
Beschreibung:Gesehen am 25.02.2026
Beschreibung:Online Resource
ISSN:1520-5126
DOI:10.1021/jacs.5c12864

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