A Comparison of Electron-Transfer Dynamics in Ionic Liquids and Neutral Solvents

The effect of ionic liquids on photoinduced electron-transfer reactions in a donor–bridge–acceptor system is examined for two ionic liquid solvents, 1-butyl-1-methylpyrrolidinium bis­(trifluoromethylsulfonyl)­amide and tributylmethylammonium bis­(trifluoromethylsulfonyl)­amide. The results are compared with those for the same system in methanol and acetonitrile solution. Electron-transfer rates were measured using time-resolved fluorescence quenching for the donor–bridge–acceptor system comprising a 1-<i>N</i>,1-<i>N</i>-dimethylbenzene-1,4-diamine donor, a proline bridge, and a coumarin 343 acceptor. The photoinduced electron-transfer processes are in the inverted regime (−Δ<i>G</i> > λ) in all four solvents, with driving forces of −1.6 to −1.9 eV and estimated reorganization energies of about 1.0 eV. The observed electron-transfer kinetics have broadly distributed rates that are generally slower in the ionic liquids compared to the neutral solvents, which also have narrower rate distributions. To describe the broad distributions of electron-transfer kinetics, we use two different models: a distribution of exponential lifetimes and a discrete sum of exponential lifetimes. Analysis of the donor–acceptor electronic coupling shows that for ionic liquids this intramolecular electron-transfer reaction should be treated using a solvent-controlled electron-transfer model