Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution
Twisted polyarenes with persistent chirality are desirable but their synthesis has remained a challenge. In this study, we present a "one-pot" synthesis of 1,2:8,9-dibenzozethrene (DBZ) and its vertically fused dimers and trimers using nickel-catalyzed cyclo-oligomerization reactions. X-ra...
| Main Authors: | , , , , , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
| Published: |
2023
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| Subjects: | |
| Online Access: | https://hdl.handle.net/10356/171753 |
| _version_ | 1826129063817773056 |
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| author | Sun, Zhitao Fan, Wei Han, Yi Yuan, Wei Ni, Yong Wang, Jinyi Wei, Haipeng Zhao, Yanli Sun, Zhe Wu, Jishan |
| author2 | School of Chemistry, Chemical Engineering and Biotechnology |
| author_facet | School of Chemistry, Chemical Engineering and Biotechnology Sun, Zhitao Fan, Wei Han, Yi Yuan, Wei Ni, Yong Wang, Jinyi Wei, Haipeng Zhao, Yanli Sun, Zhe Wu, Jishan |
| author_sort | Sun, Zhitao |
| collection | NTU |
| description | Twisted polyarenes with persistent chirality are desirable but their synthesis has remained a challenge. In this study, we present a "one-pot" synthesis of 1,2:8,9-dibenzozethrene (DBZ) and its vertically fused dimers and trimers using nickel-catalyzed cyclo-oligomerization reactions. X-ray crystallographic analysis confirmed highly twisted helical structures that consist of equal parts left- and right-handed enantiomers. Notably, the end-to-end twist between the terminal anthracene units measured 66°, 130°, and 201° for the DBZ monomer, dimer, and trimer, respectively, setting a new record among twisted polyarenes. Furthermore, the chiral resolution by HPLC yielded two enantiomers for the fused DBZ dimer and trimer, both of which maintained stable configurations and showed absorption dissymmetry factors of around 0.008-0.009. Additionally, their optical and electrochemical properties were investigated, which exhibited a chain-length dependence. |
| first_indexed | 2024-10-01T07:34:37Z |
| format | Journal Article |
| id | ntu-10356/171753 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T07:34:37Z |
| publishDate | 2023 |
| record_format | dspace |
| spelling | ntu-10356/1717532023-11-10T15:31:46Z Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution Sun, Zhitao Fan, Wei Han, Yi Yuan, Wei Ni, Yong Wang, Jinyi Wei, Haipeng Zhao, Yanli Sun, Zhe Wu, Jishan School of Chemistry, Chemical Engineering and Biotechnology Science::Chemistry Chiral Resolutions Cyclooligomerization Twisted polyarenes with persistent chirality are desirable but their synthesis has remained a challenge. In this study, we present a "one-pot" synthesis of 1,2:8,9-dibenzozethrene (DBZ) and its vertically fused dimers and trimers using nickel-catalyzed cyclo-oligomerization reactions. X-ray crystallographic analysis confirmed highly twisted helical structures that consist of equal parts left- and right-handed enantiomers. Notably, the end-to-end twist between the terminal anthracene units measured 66°, 130°, and 201° for the DBZ monomer, dimer, and trimer, respectively, setting a new record among twisted polyarenes. Furthermore, the chiral resolution by HPLC yielded two enantiomers for the fused DBZ dimer and trimer, both of which maintained stable configurations and showed absorption dissymmetry factors of around 0.008-0.009. Additionally, their optical and electrochemical properties were investigated, which exhibited a chain-length dependence. Published version J. W. acknowledges the financial support from A*STAR MTC IRG grant (M22K2c0083) and NRF Investigatorship award (NRFNRFI05-2019-0005). Z. S acknowledges financial support from National Natural Science Foundation of China (grant no. 21971187, 22222110), Natural Science Foundation of Tianjin (19JCJQJC62700) and the Haihe Laboratory of Sustainable Chemical Transformations. 2023-11-07T02:36:26Z 2023-11-07T02:36:26Z 2023 Journal Article Sun, Z., Fan, W., Han, Y., Yuan, W., Ni, Y., Wang, J., Wei, H., Zhao, Y., Sun, Z. & Wu, J. (2023). Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution. Chemical Science, 14(29), 7922-7927. https://dx.doi.org/10.1039/d3sc02285d 2041-6520 https://hdl.handle.net/10356/171753 10.1039/d3sc02285d 37502331 2-s2.0-85165486060 29 14 7922 7927 en Chemical Science © 2023 The Author(s). Published by the Royal Society of Chemistry. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. application/pdf |
| spellingShingle | Science::Chemistry Chiral Resolutions Cyclooligomerization Sun, Zhitao Fan, Wei Han, Yi Yuan, Wei Ni, Yong Wang, Jinyi Wei, Haipeng Zhao, Yanli Sun, Zhe Wu, Jishan Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution |
| title | Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution |
| title_full | Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution |
| title_fullStr | Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution |
| title_full_unstemmed | Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution |
| title_short | Helical fused 1,2:8,9-dibenzozethrene oligomers with up to 201° end-to-end twist: "one-pot" synthesis and chiral resolution |
| title_sort | helical fused 1 2 8 9 dibenzozethrene oligomers with up to 201° end to end twist one pot synthesis and chiral resolution |
| topic | Science::Chemistry Chiral Resolutions Cyclooligomerization |
| url | https://hdl.handle.net/10356/171753 |
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