Impact of charge switching stimuli on supramolecular perylene monoimide assemblies
Autor: | Monica Olvera de la Cruz, Taner Aytun, Dongxu Huang, Adam J. Dannenhoffer, Stacey M. Chin, Michael J. Bedzyk, Hiroaki Sai, Boris Harutyunyan, Daniel J. Fairfield, Benjamin Nagasing, Samuel I. Stupp |
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Rok vydání: | 2019 |
Předmět: | |
Zdroj: | Chemical Science. 10:5779-5786 |
ISSN: | 2041-6539 2041-6520 |
Popis: | 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. |
Databáze: | OpenAIRE |
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