4.8 Article

Impact of charge switching stimuli on supramolecular perylene monoimide assemblies

Journal

CHEMICAL SCIENCE
Volume 10, Issue 22, Pages 5779-5786

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/c8sc05595e

Keywords

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Funding

  1. Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, and Basic Energy Sciences [DE-SC0001059]
  2. U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-FG02-00ER45810, DE-AC02-06CH11357]
  3. Department of Energy [DE-FG02-08ER46539]
  4. Northwestern University
  5. E.I. DuPont de Nemours Co.
  6. Dow Chemical Company
  7. U.S. DOE [DE-AC02-06CH11357]
  8. So. and Hybrid Nanotechnology Experimental (SHyNE) [NSF ECCS-1542205]
  9. National Science Foundation [CHE-9871268]
  10. State of Illinois
  11. International Institute of Nanotechnology (IIN)
  12. SHyNE Resource [NSF NNCI-1542205]
  13. MRSEC program at the Materials Research Center [NSF DMR-1720139]
  14. International Institute for Nanotechnology (IIN)
  15. Keck Foundation
  16. U.S. Department of Energy (DOE) [DE-FG02-08ER46539] Funding Source: U.S. Department of Energy (DOE)

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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 x 50 x 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, H-2 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.

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