Visible-light harvesting pyrene-based MOFs as efficient ROS generators
Abstract
The utilization of reactive oxygen species (ROS) in organic transformations is of great interest due to their superior oxidative abilities under mild conditions. Recently, metal–organic frameworks (MOFs) have been developed as photosensitizers to transfer molecular oxygen to ROS for photochemical synthesis. However, visible-light responsive MOFs for oxygen activation remains scarce. Now we design and synthesize two porous MOFs, namely, PCN-822(M) (M = Zr, Hf), which are constructed by a 4,5,9,10-(K-region) substituted pyrene-based ligand, 4,4',4'',4'''-((2,7-di-tert-butylpyrene-4,5,9,10-tetrayl)tetrakis(ethyne-2,1-diyl))-tetrabenzoate (BPETB4-). With the extended π-conjugated pyrene moieties isolated on the struts, the derived MOFs are highly responsive to visible light, possessing a broad-band adsorption from 225–650 nm. As a result, the MOFs can be applied as efficient ROS generators under visible-light irradiation, and the hafnium-based MOF, PCN-822(Hf), can promote the oxidation of amines to imines by activating molecular oxygen via synergistic photo-induced energy and charge transfer.
- Authors:
-
- Department of Chemistry, Texas A&M University, College Station, USA
- Department of Environmental and Occupational Health, School of Public Health, Texas A&M University, College Station, United State
- Department of Chemistry, Texas A&M University, College Station, USA, Department of Materials Science and Engineering
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Texas A & M Univ., College Station, TX (United States); Univ. of California, Oakland, CA (United States)
- Sponsoring Org.:
- USDOE Office of Fossil Energy (FE)
- OSTI Identifier:
- 1547075
- Alternate Identifier(s):
- OSTI ID: 1614296
- Grant/Contract Number:
- FE0026472; SC0001015
- Resource Type:
- Journal Article: Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 36; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry
Citation Formats
Zhang, Yingmu, Pang, Jiandong, Li, Jialuo, Yang, Xinyu, Feng, Mingbao, Cai, Peiyu, and Zhou, Hong-Cai. Visible-light harvesting pyrene-based MOFs as efficient ROS generators. United Kingdom: N. p., 2019.
Web. doi:10.1039/C9SC03080H.
Zhang, Yingmu, Pang, Jiandong, Li, Jialuo, Yang, Xinyu, Feng, Mingbao, Cai, Peiyu, & Zhou, Hong-Cai. Visible-light harvesting pyrene-based MOFs as efficient ROS generators. United Kingdom. https://doi.org/10.1039/C9SC03080H
Zhang, Yingmu, Pang, Jiandong, Li, Jialuo, Yang, Xinyu, Feng, Mingbao, Cai, Peiyu, and Zhou, Hong-Cai. 2019.
"Visible-light harvesting pyrene-based MOFs as efficient ROS generators". United Kingdom. https://doi.org/10.1039/C9SC03080H.
@article{osti_1547075,
title = {Visible-light harvesting pyrene-based MOFs as efficient ROS generators},
author = {Zhang, Yingmu and Pang, Jiandong and Li, Jialuo and Yang, Xinyu and Feng, Mingbao and Cai, Peiyu and Zhou, Hong-Cai},
abstractNote = {The utilization of reactive oxygen species (ROS) in organic transformations is of great interest due to their superior oxidative abilities under mild conditions. Recently, metal–organic frameworks (MOFs) have been developed as photosensitizers to transfer molecular oxygen to ROS for photochemical synthesis. However, visible-light responsive MOFs for oxygen activation remains scarce. Now we design and synthesize two porous MOFs, namely, PCN-822(M) (M = Zr, Hf), which are constructed by a 4,5,9,10-(K-region) substituted pyrene-based ligand, 4,4',4'',4'''-((2,7-di-tert-butylpyrene-4,5,9,10-tetrayl)tetrakis(ethyne-2,1-diyl))-tetrabenzoate (BPETB4-). With the extended π-conjugated pyrene moieties isolated on the struts, the derived MOFs are highly responsive to visible light, possessing a broad-band adsorption from 225–650 nm. As a result, the MOFs can be applied as efficient ROS generators under visible-light irradiation, and the hafnium-based MOF, PCN-822(Hf), can promote the oxidation of amines to imines by activating molecular oxygen via synergistic photo-induced energy and charge transfer.},
doi = {10.1039/C9SC03080H},
url = {https://www.osti.gov/biblio/1547075},
journal = {Chemical Science},
issn = {2041-6520},
number = 36,
volume = 10,
place = {United Kingdom},
year = {Wed Sep 18 00:00:00 EDT 2019},
month = {Wed Sep 18 00:00:00 EDT 2019}
}
Web of Science
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