Topological classification of cycloadditions occurring on-surface and in the solid-state

The study of cycloaddition mechanisms is central to the fabrication of extended sp<sup>2</sup> carbon nanostructures such as graphene nanoribbons and spin chains. Reaction modeling in this context has focused mostly on putative, energetically preferred, exothermic products with limited consideration for symmetry allowed or forbidden mechanistic effects. To classify and optimize allowed reaction mechanisms, modern topological tools can be explored. Here, we introduce a scheme for classifying symmetry-forbidden reaction coordinates in Woodward-Hoffmann correlation diagrams. We show that topological classifiers grant access to the study of reaction pathways and correlation diagrams in the same footing, for the purpose of elucidating mechanisms and products of polycyclic aromatic azomethine ylide (PAMY) cycloadditions of pentacene-yielding polycyclic aromatic hydrocarbons with an isoindole core in the solid-state and on surfaces, as characterized by mass spectrometry and scanning tunneling microscopy, respectively. By means of a tight-binding reaction model and broken-symmetry density functional theory (DFT), we find topologically-allowed pathways for an endothermic reaction mechanism. Our work unveils topological classification as a crucial element of reaction modeling for nanographene engineering, and highlights its fundamental role in the design of cycloadditions in on-surface and solid-state chemical reactions, while underscoring that exothermic pathways can be topologically-forbidden.

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Publication Details

Journal
Communications Chemistry
Published
2025-12-03
DOI
https://doi.org/10.1038/s42004-025-01701-0
Primary Topic
Surface Chemistry and Catalysis
Type
article
Field-Weighted Citation Impact
0.00

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article

Topological classification of cycloadditions occurring on-surface and in the solid-state

Marcus Richter, Willi Auwärter, Wen‐Han Dong, Lukas Muechler et al.
Communications Chemistry
Surface Chemistry and Catalysis
article

Topological classification of cycloadditions occurring on-surface and in the solid-state

Marcus Richter, Willi Auwärter, Wen‐Han Dong, Lukas Muechler, Ji Ma, Amir Mirzanejad, Reinhard Berger, Kläus Müllen, Carlos‐Andres Palma, Johannes V. Barth, Jia‐Tao Sun, Kun Liu, Juan Li, Xinliang Feng, Xiaoye Wang
article en

Abstract

The study of cycloaddition mechanisms is central to the fabrication of extended sp<sup>2</sup> carbon nanostructures such as graphene nanoribbons and spin chains. Reaction modeling in this context has focused mostly on putative, energetically preferred, exothermic products with limited consideration for symmetry allowed or forbidden mechanistic effects. To classify and optimize allowed reaction mechanisms, modern topological tools can be explored. Here, we introduce a scheme for classifying symmetry-forbidden reaction coordinates in Woodward-Hoffmann correlation diagrams. We show that topological classifiers grant access to the study of reaction pathways and correlation diagrams in the same footing, for the purpose of elucidating mechanisms and products of polycyclic aromatic azomethine ylide (PAMY) cycloadditions of pentacene-yielding polycyclic aromatic hydrocarbons with an isoindole core in the solid-state and on surfaces, as characterized by mass spectrometry and scanning tunneling microscopy, respectively. By means of a tight-binding reaction model and broken-symmetry density functional theory (DFT), we find topologically-allowed pathways for an endothermic reaction mechanism. Our work unveils topological classification as a crucial element of reaction modeling for nanographene engineering, and highlights its fundamental role in the design of cycloadditions in on-surface and solid-state chemical reactions, while underscoring that exothermic pathways can be topologically-forbidden.

Communications ChemistryVol. 8(1)
Beijing Institute of Technology (CN), Pennsylvania State University (US), Chinese Academy of Sciences (CN), ZHAW Zurich University of Applied Sciences (CH), Beijing Electronic Science and Technology Institute (CN), Nankai University (CN), Humboldt-Universität zu Berlin (DE), Max Planck Institute for Polymer Research (DE), FZU ‒ Institute of Physics of the Academy of Sciences of the Czech Republic (CZ), Institute of Physics (CN), Zhuhai Institute of Advanced Technology (CN), Technical University of Munich (DE), Technische Universität Dresden (DE), Ministry of Industry and Information Technology (CN)
Alexander von Humboldt-Stiftung, Graphene Flagship, Deutsche Forschungsgemeinschaft, Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung, National Natural Science Foundation of China, Chinese Academy of Sciences, Technische Universität Dresden, Humboldt-Universität zu Berlin, K. C. Wong Education Foundation, National Key Research and Development Program of China
Openalex Percentile: Top 63%
Surface Chemistry and Catalysis
DOIOpen Access PDFOpenAlex
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