Impact of charge switching stimuli on supramolecular perylene monoimide assemblies
Abstract
The development of stimuli-responsive amphiphilic supramolecular nanostructures is an attractive target for systems based on light-absorbing chromophores that can function as photosensitizers in water. We report here on a water soluble supramolecular carboxylated perylene monoimide system in which charge can be switched significantly by a change in pH. This was accomplished by substituting the perylene core with an ionizable hydroxyl group. In acidic environments, crystalline supramolecular nanoribbons with dimensions on the order of 500 × 50 × 2 nm form readily, while in basic solution the additional electrostatic repulsion of the ionized hydroxyl reduces assemblies to very small dimensions on the order of only several nanometers. The HOMO/LUMO levels were also found to be sensitive to pH; in acidic media the HOMO/LUMO levels are –5.65 and –3.70 eV respectively versus vacuum, whereas is in basic conditions they are –4.90 and –3.33 eV, respectively. Utilizing the assemblies as photosensitizers in photocatalytic production of hydrogen with [Mo3S13]2– as a catalyst at a pH of 4, H2 was generated with a turnover number of 125 after 18 hours. Charge switching the assemblies at a pH of 9–10 and using an iron porphyrin catalyst, protons could again be reduced to hydrogen and CO2 wasmore »
- Authors:
-
[1];
[2];
[3];
[1];
[3];
[5];
[6];
[6]
- Department of Materials Science and Engineering, Evanston, USA
- Department of Materials Science and Engineering, Evanston, USA, Simpson Querrey Institute, Northwestern University
- Department of Chemistry, Northwestern University, Evanston, USA
- Department of Physics and Astronomy, Northwestern University, Evanston, USA
- Department of Materials Science and Engineering, Evanston, USA, Department of Physics and Astronomy, Northwestern University
- Department of Materials Science and Engineering, Evanston, USA, Department of Chemistry, Northwestern University
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1512525
- Alternate Identifier(s):
- OSTI ID: 1822214; OSTI ID: 1846655
- Grant/Contract Number:
- DEFG0200ER45810; DESC0001059; FG02-08ER46539; SC0001059; AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 22; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 99 GENERAL AND MISCELLANEOUS
Citation Formats
Dannenhoffer, Adam, Sai, Hiroaki, Huang, Dongxu, Nagasing, Benjamin, Harutyunyan, Boris, Fairfield, Daniel J., Aytun, Taner, Chin, Stacey M., Bedzyk, Michael J., Olvera de la Cruz, Monica, and Stupp, Samuel I. Impact of charge switching stimuli on supramolecular perylene monoimide assemblies. United Kingdom: N. p., 2019.
Web. doi:10.1039/C8SC05595E.
Dannenhoffer, Adam, Sai, Hiroaki, Huang, Dongxu, Nagasing, Benjamin, Harutyunyan, Boris, Fairfield, Daniel J., Aytun, Taner, Chin, Stacey M., Bedzyk, Michael J., Olvera de la Cruz, Monica, & Stupp, Samuel I. Impact of charge switching stimuli on supramolecular perylene monoimide assemblies. United Kingdom. https://doi.org/10.1039/C8SC05595E
Dannenhoffer, Adam, Sai, Hiroaki, Huang, Dongxu, Nagasing, Benjamin, Harutyunyan, Boris, Fairfield, Daniel J., Aytun, Taner, Chin, Stacey M., Bedzyk, Michael J., Olvera de la Cruz, Monica, and Stupp, Samuel I. Wed .
"Impact of charge switching stimuli on supramolecular perylene monoimide assemblies". United Kingdom. https://doi.org/10.1039/C8SC05595E.
@article{osti_1512525,
title = {Impact of charge switching stimuli on supramolecular perylene monoimide assemblies},
author = {Dannenhoffer, Adam and Sai, Hiroaki and Huang, Dongxu and Nagasing, Benjamin and Harutyunyan, Boris and Fairfield, Daniel J. and Aytun, Taner and Chin, Stacey M. and Bedzyk, Michael J. and Olvera de la Cruz, Monica and Stupp, Samuel I.},
abstractNote = {The development of stimuli-responsive amphiphilic supramolecular nanostructures is an attractive target for systems based on light-absorbing chromophores that can function as photosensitizers in water. We report here on a water soluble supramolecular carboxylated perylene monoimide system in which charge can be switched significantly by a change in pH. This was accomplished by substituting the perylene core with an ionizable hydroxyl group. In acidic environments, crystalline supramolecular nanoribbons with dimensions on the order of 500 × 50 × 2 nm form readily, while in basic solution the additional electrostatic repulsion of the ionized hydroxyl reduces assemblies to very small dimensions on the order of only several nanometers. The HOMO/LUMO levels were also found to be sensitive to pH; in acidic media the HOMO/LUMO levels are –5.65 and –3.70 eV respectively versus vacuum, whereas is in basic conditions they are –4.90 and –3.33 eV, respectively. Utilizing the assemblies as photosensitizers in photocatalytic production of hydrogen with [Mo3S13]2– as a catalyst at a pH of 4, H2 was generated with a turnover number of 125 after 18 hours. Charge switching the assemblies at a pH of 9–10 and using an iron porphyrin catalyst, protons could again be reduced to hydrogen and CO2 was reduced to CO with a turnover number of 30. The system investigated offers an example of dynamic photosensitizing assemblies that can drive reactions in both acidic and basic media.},
doi = {10.1039/C8SC05595E},
journal = {Chemical Science},
number = 22,
volume = 10,
place = {United Kingdom},
year = {Wed Jun 05 00:00:00 EDT 2019},
month = {Wed Jun 05 00:00:00 EDT 2019}
}
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