Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures
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 m...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2024-11-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-024-53927-6 |
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| author | 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 Pei-Nian Liu |
| author_facet | 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 Pei-Nian Liu |
| author_sort | Deng-Yuan Li |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-e077672d74844914933b6f0ce22fb835 |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2024-11-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-e077672d74844914933b6f0ce22fb8352025-08-20T02:50:08ZengNature PortfolioNature Communications2041-17232024-11-0115111010.1038/s41467-024-53927-6Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structuresDeng-Yuan Li0Zheng-Yang Huang1Li-Xia Kang2Bing-Xin Wang3Jian-Hui Fu4Ying Wang5Guang-Yan Xing6Yan Zhao7Xin-Yu Zhang8Pei-Nian Liu9State Key Laboratory of Natural Medicines, School of Pharmacy, China Pharmaceutical UniversitySchool of Chemistry and Molecular Engineering, East China University of Science & TechnologySchool of Chemistry and Molecular Engineering, East China University of Science & TechnologySchool of Chemistry and Molecular Engineering, East China University of Science & TechnologySchool of Chemistry and Molecular Engineering, East China University of Science & TechnologySchool of Chemistry and Molecular Engineering, East China University of Science & TechnologySchool of Chemistry and Molecular Engineering, East China University of Science & TechnologySchool of Chemistry and Molecular Engineering, East China University of Science & TechnologySchool of Chemistry and Molecular Engineering, East China University of Science & TechnologyState Key Laboratory of Natural Medicines, School of Pharmacy, China Pharmaceutical UniversityAbstract 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.https://doi.org/10.1038/s41467-024-53927-6 |
| spellingShingle | 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 Pei-Nian Liu Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures Nature Communications |
| title | Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures |
| title_full | Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures |
| title_fullStr | Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures |
| title_full_unstemmed | Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures |
| title_short | Room-temperature selective cyclodehydrogenation on Au(111) via radical addition of open-shell resonance structures |
| title_sort | room temperature selective cyclodehydrogenation on au 111 via radical addition of open shell resonance structures |
| url | https://doi.org/10.1038/s41467-024-53927-6 |
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