Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures

Deng-Yuan Li (), Zheng-Yang Huang, Li-Xia Kang, Bing-Xin Wang, Jian-Hui Fu, Ying Wang, Guang-Yan Xing, Yan Zhao, Xin-Yu Zhang and Pei-Nian Liu ()
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Deng-Yuan Li: China Pharmaceutical University
Zheng-Yang Huang: East China University of Science & Technology
Li-Xia Kang: East China University of Science & Technology
Bing-Xin Wang: East China University of Science & Technology
Jian-Hui Fu: East China University of Science & Technology
Ying Wang: East China University of Science & Technology
Guang-Yan Xing: East China University of Science & Technology
Yan Zhao: East China University of Science & Technology
Xin-Yu Zhang: East China University of Science & Technology
Pei-Nian Liu: China Pharmaceutical University

Nature Communications, 2024, vol. 15, issue 1, 1-10

Abstract: Abstract Cyclodehydrogenation is an important ring-formation reaction that can directly produce planar-conjugated carbon-based nanomaterials from nonplanar molecules. However, inherently high C–H bond energy necessitates a high temperature during dehydrogenation, and the ubiquity of C − H bonds in molecules and small differences in their bond energies hinder the selectivity of dehydrogenation. Here, we report a room-temperature cyclodehydrogenation reaction on Au(111) via radical addition of open-shell resonance structures and demonstrate that radical addition significantly decreases cyclodehydrogenation temperature and further improves the chemoselectivity of dehydrogenation. Using scanning tunneling microscopy and non-contact atomic force microscopy, we visualize the cascade reaction process involved in cyclodehydrogenation and determine atomic structures and molecular orbitals of the planar acetylene-linked oxa-nanographene products. The nonplanar intermediates observed during progression annealing, combined with density functional theory calculations, suggest that room-temperature cyclodehydrogenation involves the formation of transient radicals, intramolecular radical addition, and hydrogen elimination; and that the high chemoselectivity of cyclodehydrogenation arises from the reversibility and different thermodynamics of radical addition step.

Date: 2024
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DOI: 10.1038/s41467-024-53927-6

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