Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers
Currently, the most popular molecular photosensitizers used for synthetic organic chemistry and energy applications are still the noble metal-based ruthenium and iridium complexes that usually require expensive metal and ligand precursors. In contrast, bis(arylimino)acenaphthene (Ar-BIAN) are establ...
| Main Authors: | , , , , , , , |
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| Format: | Journal Article |
| Language: | English |
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2018
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| Online Access: | https://hdl.handle.net/10356/87653 http://hdl.handle.net/10220/46916 |
| _version_ | 1826111255677501440 |
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| author | Ng, Yik Yie Tan, Lisa Jiaying Ng, Shue Mei Chai, Yoke Tin Ganguly, Rakesh Du, Yonghua Yeow, Edwin Kok Lee Soo, Han Sen |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Ng, Yik Yie Tan, Lisa Jiaying Ng, Shue Mei Chai, Yoke Tin Ganguly, Rakesh Du, Yonghua Yeow, Edwin Kok Lee Soo, Han Sen |
| author_sort | Ng, Yik Yie |
| collection | NTU |
| description | Currently, the most popular molecular photosensitizers used for synthetic organic chemistry and energy applications are still the noble metal-based ruthenium and iridium complexes that usually require expensive metal and ligand precursors. In contrast, bis(arylimino)acenaphthene (Ar-BIAN) are established redox non-innocent π-accepting ligands that are easily assembled in one condensation step from affordable and commercially available precursors. Herein, we have developed a series of Ar-BIAN Cu(I) complexes as visible light harvesting photosensitizers. Notably, one of these panchromatic, homoleptic Ar-BIAN Cu(I) complexes exhibits a radiative recombination lifetime that is longer than diffusion control, as observed by time-correlated single photon counting spectroscopy. The Ar-BIAN Cu(I) facilitates visible-light promoted atom transfer radical addition reactions via carbon-carbon bond formation with CBr3 radicals in good yields of up to 75%. Steady-state and transient absorption spectroscopic measurements, together with spectroelectrochemical experiments and intermediate isolation studies, were performed to obtain insights into this photoredox catalysis and provide guidelines for the general deployment of Ar-BIAN Cu(I) photosensitizers in synthetic organic chemistry and renewable energy applications. |
| first_indexed | 2024-10-01T02:47:42Z |
| format | Journal Article |
| id | ntu-10356/87653 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T02:47:42Z |
| publishDate | 2018 |
| record_format | dspace |
| spelling | ntu-10356/876532023-02-28T19:23:44Z Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers Ng, Yik Yie Tan, Lisa Jiaying Ng, Shue Mei Chai, Yoke Tin Ganguly, Rakesh Du, Yonghua Yeow, Edwin Kok Lee Soo, Han Sen School of Physical and Mathematical Sciences Copper Photosensitizer Bis(arylimino)acenaphthene DRNTU::Science::Chemistry Currently, the most popular molecular photosensitizers used for synthetic organic chemistry and energy applications are still the noble metal-based ruthenium and iridium complexes that usually require expensive metal and ligand precursors. In contrast, bis(arylimino)acenaphthene (Ar-BIAN) are established redox non-innocent π-accepting ligands that are easily assembled in one condensation step from affordable and commercially available precursors. Herein, we have developed a series of Ar-BIAN Cu(I) complexes as visible light harvesting photosensitizers. Notably, one of these panchromatic, homoleptic Ar-BIAN Cu(I) complexes exhibits a radiative recombination lifetime that is longer than diffusion control, as observed by time-correlated single photon counting spectroscopy. The Ar-BIAN Cu(I) facilitates visible-light promoted atom transfer radical addition reactions via carbon-carbon bond formation with CBr3 radicals in good yields of up to 75%. Steady-state and transient absorption spectroscopic measurements, together with spectroelectrochemical experiments and intermediate isolation studies, were performed to obtain insights into this photoredox catalysis and provide guidelines for the general deployment of Ar-BIAN Cu(I) photosensitizers in synthetic organic chemistry and renewable energy applications. ASTAR (Agency for Sci., Tech. and Research, S’pore) MOE (Min. of Education, S’pore) Accepted version 2018-12-11T09:22:17Z 2019-12-06T16:46:31Z 2018-12-11T09:22:17Z 2019-12-06T16:46:31Z 2018 Journal Article Ng, Y. Y., Tan, L. J., Ng, S. M., Chai, Y. T., Ganguly, R., Du, Y., Yeow, E. K. L., & Soo, H. S. (2018). Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers. ACS Catalysis, 11277-11286. doi:10.1021/acscatal.8b02502 https://hdl.handle.net/10356/87653 http://hdl.handle.net/10220/46916 10.1021/acscatal.8b02502 en ACS Catalysis © 2018 American Chemical Society (ACS). This is the author created version of a work that has been peer reviewed and accepted for publication by ACS Catalysis, American Chemical Society (ACS). It incorporates referee’s comments but changes resulting from the publishing process, such as copyediting, structural formatting, may not be reflected in this document. The published version is available at: [http://dx.doi.org/10.1021/acscatal.8b02502]. 11 p. application/pdf |
| spellingShingle | Copper Photosensitizer Bis(arylimino)acenaphthene DRNTU::Science::Chemistry Ng, Yik Yie Tan, Lisa Jiaying Ng, Shue Mei Chai, Yoke Tin Ganguly, Rakesh Du, Yonghua Yeow, Edwin Kok Lee Soo, Han Sen Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers |
| title | Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers |
| title_full | Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers |
| title_fullStr | Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers |
| title_full_unstemmed | Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers |
| title_short | Spectroscopic characterization and mechanistic studies on visible light photoredox carbon–carbon bond formation by bis(arylimino)acenaphthene copper photosensitizers |
| title_sort | spectroscopic characterization and mechanistic studies on visible light photoredox carbon carbon bond formation by bis arylimino acenaphthene copper photosensitizers |
| topic | Copper Photosensitizer Bis(arylimino)acenaphthene DRNTU::Science::Chemistry |
| url | https://hdl.handle.net/10356/87653 http://hdl.handle.net/10220/46916 |
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