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Water-Triggered Photoinduced Electron Transfer in Acetonitrile-Water Binary Solvent : Solvent Microstructure-Tuned Reactivity of Hydrophobic Solutes

Title data

Lewnadowska-Andralojc, Anna ; Hug, Gordon ; Marciniak, Bronislaw ; Hörner, Gerald ; Swiatla-Wojcik, Dorota:
Water-Triggered Photoinduced Electron Transfer in Acetonitrile-Water Binary Solvent : Solvent Microstructure-Tuned Reactivity of Hydrophobic Solutes.
In: The Journal of Physical Chemistry B. (June 2020) . - online publ..
ISSN 1520-5207
DOI: https://doi.org/10.1021/acs.jpcb.0c02635

Project information

Project financing: Deutsche Forschungsgemeinschaft

Abstract in another language

The solvent-composition dependence of quenching triplet states of benzophenone (3BP) by anisole in acetonitrile-water (ACN-H2O) mixtures was investigated by laser flash photolysis over the water mole fraction (xw) increasing from 0 to 0.92. Single exponential decay of 3BP was observed over the whole composition range. The quenching rate constant consistently increased with the water content but increased far more rapidly with xw > 0.7. The water-triggered electron transfer (ET) mechanism was confirmed by a steeply growing quantum yield of the BP ketyl radical anion, escaping back electron transfer when the partial water volume exceeded the acetonitrile one. The water-content influence on the 3BP quenching-rate was described by a kinetic model accounting for the microheterogeneous structure of the ACN-H2O mixtures and the very different solubility of the reactants in the solvent components. According to the model the ET mechanism occurs at a rate constant of 1.46 x 109 M-1s-1 and is presumably assisted by the ACN-H2O hydrogen-bonding interaction.

Further data

Item Type: Article in a journal
Refereed: Yes
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Chemistry > Chair Inorganic Chemistry IV > Chair Inorganic Chemistry IV - Univ.-Prof. Dr. Birgit Weber
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 540 Chemistry
Date Deposited: 25 Jun 2020 07:07
Last Modified: 25 Jun 2020 07:07
URI: https://eref.uni-bayreuth.de/id/eprint/55616