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Title: 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:
 [1];  [1]; ORCiD logo [1];  [1];  [2];  [1]; ORCiD logo [3]
  1. Department of Chemistry, Texas A&M University, College Station, USA
  2. Department of Environmental and Occupational Health, School of Public Health, Texas A&M University, College Station, United State
  3. Department of Chemistry, Texas A&M University, College Station, USA, Department of Materials Science and Engineering
Publication Date:
Research Org.:
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:
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. doi:10.1039/C9SC03080H.
Zhang, Yingmu, Pang, Jiandong, Li, Jialuo, Yang, Xinyu, Feng, Mingbao, Cai, Peiyu, and Zhou, Hong-Cai. Wed . "Visible-light harvesting pyrene-based MOFs as efficient ROS generators". United Kingdom. doi: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},
journal = {Chemical Science},
number = 36,
volume = 10,
place = {United Kingdom},
year = {2019},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9SC03080H

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Cited by: 4 works
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