The impact of solvent dynamics on intermolecular electron transfer has been well studied in neat electron donor solvents such as amines and anilines; however virtually no studies of this sort have been conducted in ionic liquids. The high viscosities of ionic liquids lead to much slower solvent dynamics, and presumably to significant differences in electron transfer to/from these solvents. In this study, steady-state and time-resolved emission methods were used to measure electron transfer quenching between excited-state coumarin electron donors and electron acceptor pyridinium cations in both dilute solution and neat in pyridinium ionic liquids. Stern-Volmer analyses of quenching in dilute solutions of acetonitrile and dimethylsulfoxide showed a wide range of quenching rates for different coumarin dyes that correlated well to estimated free energies of excited-state oxidation. Time-resolved measurements in neat ionic liquid accepting solvents also show marked differences in quenching rates.  In these cases, only local rearrangements, rather than diffusive transport of species is necessary for electron transfer.  It is hoped that such experiments will shed new light on dynamics in ionic liquids.

Intermolecular electron transfer in neat pyridinium ionic liquids

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.