Impact of charge switching stimuli on supramolecular perylene monoimide assemblies.

Autor: Dannenhoffer A; Department of Materials Science and Engineering , 2220 Campus Drive , Evanston , IL 60208 , USA., Sai H; Department of Materials Science and Engineering , 2220 Campus Drive , Evanston , IL 60208 , USA.; Simpson Querrey Institute , Northwestern University , 303 E. Superior , Chicago , Illinois 60611 , USA., Huang D; Department of Materials Science and Engineering , 2220 Campus Drive , Evanston , IL 60208 , USA., Nagasing B; Department of Chemistry , Northwestern University , 2145 Sheridan Road , Evanston , IL 60208 , USA . Email: s-stupp@northwestern.edu., Harutyunyan B; Department of Physics and Astronomy , Northwestern University , 2145 Sheridan Road , Evanston , IL 60208 , USA., Fairfield DJ; Department of Materials Science and Engineering , 2220 Campus Drive , Evanston , IL 60208 , USA., Aytun T; Department of Materials Science and Engineering , 2220 Campus Drive , Evanston , IL 60208 , USA., Chin SM; Department of Chemistry , Northwestern University , 2145 Sheridan Road , Evanston , IL 60208 , USA . Email: s-stupp@northwestern.edu., Bedzyk MJ; Department of Materials Science and Engineering , 2220 Campus Drive , Evanston , IL 60208 , USA.; Department of Physics and Astronomy , Northwestern University , 2145 Sheridan Road , Evanston , IL 60208 , USA., Olvera de la Cruz M; Department of Materials Science and Engineering , 2220 Campus Drive , Evanston , IL 60208 , USA.; Department of Chemistry , Northwestern University , 2145 Sheridan Road , Evanston , IL 60208 , USA . Email: s-stupp@northwestern.edu., Stupp SI; Department of Materials Science and Engineering , 2220 Campus Drive , Evanston , IL 60208 , USA.; Department of Chemistry , Northwestern University , 2145 Sheridan Road , Evanston , IL 60208 , USA . Email: s-stupp@northwestern.edu.; Department of Medicine , Northwestern University , 676 N St. Clair , Chicago , Illinois 60611 , USA.; Simpson Querrey Institute , Northwestern University , 303 E. Superior , Chicago , Illinois 60611 , USA.; Department of Biomedical Engineering , Northwestern University , 2145 Sheridan Road , Evanston , IL 60208 , USA.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2019 May 14; Vol. 10 (22), pp. 5779-5786. Date of Electronic Publication: 2019 May 14 (Print Publication: 2019).
DOI: 10.1039/c8sc05595e
Abstrakt: 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 [Mo 3 S 13 ] 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 CO 2 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.
Databáze: MEDLINE
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