Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern
The first family of extended and fluorinated corannulenes is prepared through a highly efficient and modular synthetic strategy. In this strategy, corannulene aldehyde could be combined with the fluorine-carrying phosphonium ylides to furnish stilbene-like vinylene precursors. A photochemically indu...
| Main Authors: | , , , , , |
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| Other Authors: | |
| Format: | Journal Article |
| Language: | English |
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2020
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| Online Access: | https://hdl.handle.net/10356/137633 |
| _version_ | 1826128970190422016 |
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| author | Halilovic, Dzeneta Budanović, Maja Wong, Zeng R. Webster, Richard David Huh, June Stuparu, Mihaiela Corina |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Halilovic, Dzeneta Budanović, Maja Wong, Zeng R. Webster, Richard David Huh, June Stuparu, Mihaiela Corina |
| author_sort | Halilovic, Dzeneta |
| collection | NTU |
| description | The first family of extended and fluorinated corannulenes is prepared through a highly efficient and modular synthetic strategy. In this strategy, corannulene aldehyde could be combined with the fluorine-carrying phosphonium ylides to furnish stilbene-like vinylene precursors. A photochemically induced oxidative cyclization process of these precursors gives rise to the fluorinated and curved polycyclic aromatic hydrocarbons. A UV-vis absorption study shows that aromatic extension results in a bathochromic shift of about 12 nm. Fluorination further shifts the absorption spectrum to the red region, and a maximum shift of about 22 nm is detected for a compound carrying two trifluoromethyl groups. A cyclic and square-wave voltammetry investigation reveals that the extension of the corannulene scaffold increases the reduction potential by 0.11 V. Placement of fluorine or trifluoromethyl groups further enhances the electron affinities. In this regard, the presence of one trifluoromethyl group equals the effect of three aromatic fluorine atoms. Molecules with two trifluoromethyl groups, meanwhile, exhibit the highest reduction potentials of -1.93 and -1.83 V. These values are 0.37 and 0.46 V higher than those of the parental corannulene and demonstrate the utility of the present design concept by efficiently accessing effective electron acceptors based on the buckybowl motif. |
| first_indexed | 2024-10-01T07:33:12Z |
| format | Journal Article |
| id | ntu-10356/137633 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T07:33:12Z |
| publishDate | 2020 |
| record_format | dspace |
| spelling | ntu-10356/1376332023-12-06T05:45:20Z Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern Halilovic, Dzeneta Budanović, Maja Wong, Zeng R. Webster, Richard David Huh, June Stuparu, Mihaiela Corina School of Physical and Mathematical Sciences Science::Chemistry Fluorinated Corannulene Vinylene Precursors The first family of extended and fluorinated corannulenes is prepared through a highly efficient and modular synthetic strategy. In this strategy, corannulene aldehyde could be combined with the fluorine-carrying phosphonium ylides to furnish stilbene-like vinylene precursors. A photochemically induced oxidative cyclization process of these precursors gives rise to the fluorinated and curved polycyclic aromatic hydrocarbons. A UV-vis absorption study shows that aromatic extension results in a bathochromic shift of about 12 nm. Fluorination further shifts the absorption spectrum to the red region, and a maximum shift of about 22 nm is detected for a compound carrying two trifluoromethyl groups. A cyclic and square-wave voltammetry investigation reveals that the extension of the corannulene scaffold increases the reduction potential by 0.11 V. Placement of fluorine or trifluoromethyl groups further enhances the electron affinities. In this regard, the presence of one trifluoromethyl group equals the effect of three aromatic fluorine atoms. Molecules with two trifluoromethyl groups, meanwhile, exhibit the highest reduction potentials of -1.93 and -1.83 V. These values are 0.37 and 0.46 V higher than those of the parental corannulene and demonstrate the utility of the present design concept by efficiently accessing effective electron acceptors based on the buckybowl motif. 2020-04-07T03:54:11Z 2020-04-07T03:54:11Z 2018 Journal Article Halilovic, D., Budanovic, M., Wong, Z. R., Webster, R. D., Huh, J., & Stuparu. M. C. (2018). Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern. Journal of organic chemistry, 83(7), 3529-3536. doi:10.1021/acs.joc.7b03146 0022-3263 https://hdl.handle.net/10356/137633 10.1021/acs.joc.7b03146 29518317 2-s2.0-85045118514 7 83 3529 3536 en Journal of organic chemistry © 2018 American Chemical Society. All rights reserved. |
| spellingShingle | Science::Chemistry Fluorinated Corannulene Vinylene Precursors Halilovic, Dzeneta Budanović, Maja Wong, Zeng R. Webster, Richard David Huh, June Stuparu, Mihaiela Corina Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern |
| title | Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern |
| title_full | Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern |
| title_fullStr | Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern |
| title_full_unstemmed | Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern |
| title_short | Photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern |
| title_sort | photochemical synthesis and electronic properties of extended corannulenes with variable fluorination pattern |
| topic | Science::Chemistry Fluorinated Corannulene Vinylene Precursors |
| url | https://hdl.handle.net/10356/137633 |
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