Chiral stacks of a curved nanographene
Despite enormous advances in the edge extension chemistry of nanographenes, examples of peri-annulations and the knowledge of their effect on molecular properties remain scarce. Here, we show the synthesis of a curved C60S5 nanographene comprising quintuple [5]thiahelicenes arranged in a C5-symmetri...
| Main Authors: | , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2024
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/180414 |
| _version_ | 1826127928848547840 |
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| author | Zhang, Zhongbo Csókás, Daniel Fernández, Israel Stuparu, Mihaiela Corina |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Zhang, Zhongbo Csókás, Daniel Fernández, Israel Stuparu, Mihaiela Corina |
| author_sort | Zhang, Zhongbo |
| collection | NTU |
| description | Despite enormous advances in the edge extension chemistry of nanographenes, examples of peri-annulations and the knowledge of their effect on molecular properties remain scarce. Here, we show the synthesis of a curved C60S5 nanographene comprising quintuple [5]thiahelicenes arranged in a C5-symmetric fashion on the zigzag edge (L-region) of a bowl-shaped corannulene core. The synthesis is achieved with the help of Stille coupling, alkynyl thiolation, sulfide/aryne cyclization, and direct arylation reactions. The prepared bowl-helix chiral structure absorbs and emits in the visible and near-IR regions. It assembles into persistent molecular bilayer graphene stacks in solution, solid state, and gas phase. The concave cavities of the supramolecular dimers can recognize the convex surfaces of fullerene C60 through shape complementarity and π-π stacking interactions in the solid state. A properties comparison with ortho-annulated analogs and archetypical nanographenes indicates the superiority of peri-annulations in the design of molecular graphenes. |
| first_indexed | 2025-03-09T14:41:44Z |
| format | Journal Article |
| id | ntu-10356/180414 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2025-03-09T14:41:44Z |
| publishDate | 2024 |
| record_format | dspace |
| spelling | ntu-10356/1804142024-10-11T15:31:55Z Chiral stacks of a curved nanographene Zhang, Zhongbo Csókás, Daniel Fernández, Israel Stuparu, Mihaiela Corina School of Chemistry, Chemical Engineering and Biotechnology Chemistry Molecular graphene bilayers Nanographene synthesis Despite enormous advances in the edge extension chemistry of nanographenes, examples of peri-annulations and the knowledge of their effect on molecular properties remain scarce. Here, we show the synthesis of a curved C60S5 nanographene comprising quintuple [5]thiahelicenes arranged in a C5-symmetric fashion on the zigzag edge (L-region) of a bowl-shaped corannulene core. The synthesis is achieved with the help of Stille coupling, alkynyl thiolation, sulfide/aryne cyclization, and direct arylation reactions. The prepared bowl-helix chiral structure absorbs and emits in the visible and near-IR regions. It assembles into persistent molecular bilayer graphene stacks in solution, solid state, and gas phase. The concave cavities of the supramolecular dimers can recognize the convex surfaces of fullerene C60 through shape complementarity and π-π stacking interactions in the solid state. A properties comparison with ortho-annulated analogs and archetypical nanographenes indicates the superiority of peri-annulations in the design of molecular graphenes. Ministry of Education (MOE) Published version M.C.S. acknowledges financial support from the Ministry of Education Singapore under the AcRF Tier 2 (MOE-T2EP10221-0002) and funding from the Ministry of Research, Innovation, and Digitalization under Romania’s National Recovery and Resilience Plan PNRR-III-C9-2022–I8 program, project code 167/15.11.22. I.F. acknowledges financial support from Spanish MCIN/AEI/10.13039/501100011033 (grants PID2019-106184GB-I00 and PID2022-139318NB-I00). D.C. thanks the Hungarian National Research, Development, and Innovation Office—NKFIH for grant funding (PD-146252). 2024-10-07T05:21:56Z 2024-10-07T05:21:56Z 2024 Journal Article Zhang, Z., Csókás, D., Fernández, I. & Stuparu, M. C. (2024). Chiral stacks of a curved nanographene. Chem. https://dx.doi.org/10.1016/j.chempr.2024.07.008 2451-9308 https://hdl.handle.net/10356/180414 10.1016/j.chempr.2024.07.008 2-s2.0-85203053759 en MOE-T2EP10221-0002 Chem © 2024 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY-NC license (http://creativecommons.org/licenses/by-nc/4.0/). application/pdf |
| spellingShingle | Chemistry Molecular graphene bilayers Nanographene synthesis Zhang, Zhongbo Csókás, Daniel Fernández, Israel Stuparu, Mihaiela Corina Chiral stacks of a curved nanographene |
| title | Chiral stacks of a curved nanographene |
| title_full | Chiral stacks of a curved nanographene |
| title_fullStr | Chiral stacks of a curved nanographene |
| title_full_unstemmed | Chiral stacks of a curved nanographene |
| title_short | Chiral stacks of a curved nanographene |
| title_sort | chiral stacks of a curved nanographene |
| topic | Chemistry Molecular graphene bilayers Nanographene synthesis |
| url | https://hdl.handle.net/10356/180414 |
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