title: Bimolecular photoinduced electron transfer in imidazolium-based room-temperature ionic liquids is not faster than in conventional solvents.
abstract: The fluorescence quenching of 3-cyanoperylene upon electron transfer from N,N-dimethylaniline in three room-temperature ionic liquids (RTILs) and in binary solvent mixtures of identical viscosity has been investigated using steady-state and time-resolved fluorescence spectroscopy. This study was stimulated by previous reports of bimolecular electron transfer reactions faster by one or several orders of magnitude in RTILs than in conventional polar solvents. These conclusions were usually based on a comparison with data obtained in low-viscous organic solvents and extrapolated to higher viscosities and not by performing experiments at similar viscosities as those of the RTILs, which we show to be essential. Our results reveal that (i) the diffusive motion of solutes in both types of solvents is comparable, (ii) the intrinsic electron transfer step is controlled by the solvent dynamics in both cases, being slower in the RTILs than in the conventional organic solvent of similar viscosity, and (iii) the previously reported reaction rates much larger than the diffusion limit at low quencher concentration in RTILs originate from a neglect of the static and transient stages of the quenching, which are dominant in solvents as viscous as RTILs.
authors.affiliation: Department of Physical Chemistry, University of Geneva, 30 Quai Ernest-Ansermet, 1211, Genève 4, Switzerland.
authors.forename: Marius
authors.initials: M
authors.lastname: Koch
authors.forename: Arnulf
authors.initials: A
authors.lastname: Rosspeintner
authors.forename: Gonzalo
authors.initials: G
authors.lastname: Angulo
authors.forename: Eric
authors.initials: E
authors.lastname: Vauthey
mesh_terms: D000814:Aniline Compounds / Q000737:chemistry*; D004579:Electron Transport; D052578:Ionic Liquids / Q000737:chemistry*; D010569:Perylene / Q000031:analogs & derivatives / Q000737:chemistry*; D055668:Photochemical Processes; D012997:Solvents / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013696:Temperature; D014783:Viscosity
chemical_list: D000814:Aniline Compounds; D052578:Ionic Liquids; D012997:Solvents; D010569:Perylene; C015157:N,N-dimethylaniline