Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy
Heteroatom-embedded hexa-peri-hexabenzocoronene (HBC) molecules exhibit interesting properties depending on the number and position of the introduced heteroatoms and are promising materials for applications in organic electronics and supramolecular chemistry. However, their synthesis is quite limite...
| Main Authors: | , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2024
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| Online Access: | https://hdl.handle.net/10356/180681 |
| _version_ | 1824454932651048960 |
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| author | Zhang, Xinjiang Li, Donglin Tan, Cheryl Cai Hui Hanindita, Fiona Hamamoto, Yosuke Foster, Adam S. Kawai, Shigeki Ito, Shingo |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Zhang, Xinjiang Li, Donglin Tan, Cheryl Cai Hui Hanindita, Fiona Hamamoto, Yosuke Foster, Adam S. Kawai, Shigeki Ito, Shingo |
| author_sort | Zhang, Xinjiang |
| collection | NTU |
| description | Heteroatom-embedded hexa-peri-hexabenzocoronene (HBC) molecules exhibit interesting properties depending on the number and position of the introduced heteroatoms and are promising materials for applications in organic electronics and supramolecular chemistry. However, their synthesis is quite limited because of the difficulty in selectively introducing heteroatoms into the HBC core, which poses a challenge in organic synthesis. Here we report a strategy for the in-solution synthesis of 3a2-azahexa-peri-hexabenzocoronenium salts, which are cationic nitrogen-embedded HBC derivatives. The synthesis was enabled by the formal [3 + 3] cycloaddition of polycyclic aromatic azomethine ylides with cyclopropenes, as a three-atom dipolarophile, followed by mechanochemical intramolecular cyclization. Furthermore, on-surface polymerization of aza-HBC precursors was performed to synthesize aza-HBC-based chevron-like graphene nanoribbons. This study provides the possibility for the further use of nitrogen-embedded HBC derivatives in a variety of potential applications. |
| first_indexed | 2025-02-19T03:30:10Z |
| format | Journal Article |
| id | ntu-10356/180681 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2025-02-19T03:30:10Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1806812024-10-21T01:06:10Z Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy Zhang, Xinjiang Li, Donglin Tan, Cheryl Cai Hui Hanindita, Fiona Hamamoto, Yosuke Foster, Adam S. Kawai, Shigeki Ito, Shingo School of Chemistry, Chemical Engineering and Biotechnology Chemistry Nitrogen Nanographene Heteroatom-embedded hexa-peri-hexabenzocoronene (HBC) molecules exhibit interesting properties depending on the number and position of the introduced heteroatoms and are promising materials for applications in organic electronics and supramolecular chemistry. However, their synthesis is quite limited because of the difficulty in selectively introducing heteroatoms into the HBC core, which poses a challenge in organic synthesis. Here we report a strategy for the in-solution synthesis of 3a2-azahexa-peri-hexabenzocoronenium salts, which are cationic nitrogen-embedded HBC derivatives. The synthesis was enabled by the formal [3 + 3] cycloaddition of polycyclic aromatic azomethine ylides with cyclopropenes, as a three-atom dipolarophile, followed by mechanochemical intramolecular cyclization. Furthermore, on-surface polymerization of aza-HBC precursors was performed to synthesize aza-HBC-based chevron-like graphene nanoribbons. This study provides the possibility for the further use of nitrogen-embedded HBC derivatives in a variety of potential applications. Ministry of Education (MOE) Nanyang Technological University This work was supported by Nanyang Technological University (NTU), the Ministry of Education, Singapore, under its Academic Research Fund Tier 1 (RG2/23) for S.I. and the Japan Society for the Promotion of Science (JSPS) KAKENHI grant number 22H00285 for S.K. Computing resources from the NTU High Performance Computing Team are gratefully acknowledged. We thank Y. Li (NTU) for his support with the X-ray difraction analysis and O. J. Silveira (Aalto University) for valuable discussion on the theoretical calculations. 2024-10-21T01:06:10Z 2024-10-21T01:06:10Z 2024 Journal Article Zhang, X., Li, D., Tan, C. C. H., Hanindita, F., Hamamoto, Y., Foster, A. S., Kawai, S. & Ito, S. (2024). Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy. Nature Synthesis, 3(10), 1283-1291. https://dx.doi.org/10.1038/s44160-024-00595-5 2731-0582 https://hdl.handle.net/10356/180681 10.1038/s44160-024-00595-5 2-s2.0-85198057706 10 3 1283 1291 en RG2/23 Nature Synthesis © 2024 The Author(s), under exclusive licence to Springer Nature Limited. All rights reserved. |
| spellingShingle | Chemistry Nitrogen Nanographene Zhang, Xinjiang Li, Donglin Tan, Cheryl Cai Hui Hanindita, Fiona Hamamoto, Yosuke Foster, Adam S. Kawai, Shigeki Ito, Shingo Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy |
| title | Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy |
| title_full | Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy |
| title_fullStr | Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy |
| title_full_unstemmed | Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy |
| title_short | Synthesis of azahexabenzocoronenium salts through a formal [3 + 3] cycloaddition strategy |
| title_sort | synthesis of azahexabenzocoronenium salts through a formal 3 3 cycloaddition strategy |
| topic | Chemistry Nitrogen Nanographene |
| url | https://hdl.handle.net/10356/180681 |
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