skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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.:
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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1039/C9SC03080H

Citation Metrics:
Cited by: 40 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Highly efficient visible-light-driven CO 2 reduction to formate by a new anthracene-based zirconium MOF via dual catalytic routes
journal, January 2016


Photosensitized singlet oxygen and its applications
journal, November 2002


Effect of oxygen-enhanced intersystem crossing on the observed efficiency of formation of singlet oxygen
journal, January 1990


Highly Efficient Oxidation of Amines to Imines by Singlet Oxygen and Its Application in Ugi-Type Reactions
journal, October 2009


Visible-light-assisted aerobic photocatalytic oxidation of amines to imines over NH2-MIL-125(Ti)
journal, March 2015


Luminescent sensors based on metal-organic frameworks
journal, January 2018


Nanoscale Metal–Organic Framework for Highly Effective Photodynamic Therapy of Resistant Head and Neck Cancer
journal, November 2014


Visible Light Photoredox Catalysis with Transition Metal Complexes: Applications in Organic Synthesis
journal, March 2013


Enzyme–MOF (metal–organic framework) composites
journal, January 2017


Photochemically Produced Singlet Oxygen: Applications and Perspectives
journal, June 2018


Multifunctional metal–organic framework catalysts: synergistic catalysis and tandem reactions
journal, January 2017


Photochromic Metal-Organic Frameworks: Reversible Control of Singlet Oxygen Generation
journal, December 2014


Selective Photooxidation of a Mustard-Gas Simulant Catalyzed by a Porphyrinic Metal-Organic Framework
journal, June 2015


Metallophthalocyanine-Based Conjugated Microporous Polymers as Highly Efficient Photosensitizers for Singlet Oxygen Generation
journal, April 2015


Porphyrin-Metalation-Mediated Tuning of Photoredox Catalytic Properties in Metal–Organic Frameworks
journal, August 2015


An Exceptionally Stable, Porphyrinic Zr Metal–Organic Framework Exhibiting pH-Dependent Fluorescence
journal, September 2013


Photophysical properties and applications of coordination complexes incorporating pyrene
journal, January 2015


Triplet photosensitizers: from molecular design to applications
journal, January 2013


REACTIVE OXYGEN SPECIES: Metabolism, Oxidative Stress, and Signal Transduction
journal, June 2004


Hydrogen Storage in Microporous Metal-Organic Frameworks
journal, May 2003


Synthesis and Photophysical Properties of Pyrene-Based Light-Emitting Monomers: Highly Pure-Blue-Fluorescent, Cruciform-Shaped Architectures
journal, November 2009


C 70 as a Photocatalyst for Oxidation of Secondary Benzylamines to Imines
journal, December 2015


Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production
journal, March 2016


[Ti 8 Zr 2 O 12 (COO) 16 ] Cluster: An Ideal Inorganic Building Unit for Photoactive Metal–Organic Frameworks
journal, November 2017


Singlet Oxygen Promoted Carbon−Heteroatom Bond Cleavage in Dibenzyl Sulfides and Tertiary Dibenzylamines. Structural Effects and the Role of Exciplexes
journal, December 2007


Metal-Organic Frameworks for Energy Applications
journal, January 2017


New Reactions of IBX: Oxidation of Nitrogen- and Sulfur-Containing Substrates To Afford Useful Synthetic Intermediates
journal, September 2003


Detoxification of a Sulfur Mustard Simulant Using a BODIPY-Functionalized Zirconium-Based Metal–Organic Framework
journal, July 2017


Chemistry and biology of reactive oxygen species in signaling or stress responses
journal, July 2011


Metal–organic frameworks for artificial photosynthesis and photocatalysis
journal, January 2014


4,5,9,10-Pyrene Diimides: A Family of Aromatic Diimides Exhibiting High Electron Mobility and Two-Photon Excited Emission
journal, September 2017


Catalytic Zirconium/Hafnium-Based Metal–Organic Frameworks
journal, December 2016


Visible-light harvesting iridium complexes as singlet oxygen sensitizers for photooxidation of 1,5-dihydroxynaphthalene
journal, January 2012


Photocatalytic Hydrogen Production Coupled with Selective Benzylamine Oxidation over MOF Composites
journal, March 2018


Aerobic Oxidative Coupling of Amines by Carbon Nitride Photocatalysis with Visible Light
journal, December 2010


Efficient and selective oxidation of sulfur mustard using singlet oxygen generated by a pyrene-based metal–organic framework
journal, January 2016


Recent Advances in Aerobic Oxidation of Alcohols and Amines to Imines
journal, September 2015


Singlet Oxygen Production in Water:  Aggregation and Charge-Transfer Effects
journal, January 1996


MOFs as proton conductors – challenges and opportunities
journal, January 2014


Metal–Organic Frameworks for Separations
journal, September 2011


Methane storage in flexible metal–organic frameworks with intrinsic thermal management
journal, October 2015


Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999


Visible-Light-Promoted Selective Oxidation of Alcohols Using a Covalent Triazine Framework
journal, July 2017


Reactive oxygen species generating systems meeting challenges of photodynamic cancer therapy
journal, January 2016


Controlled Generation of Singlet Oxygen in Living Cells with Tunable Ratios of the Photochromic Switch in Metal-Organic Frameworks
journal, April 2016