Pulse radiolysis study of ion-species effects on the solvated electron in alkylammonium ionic liquids

The spectra and kinetic behavior of solvated electrons (esol−) in alkyl ammonium ionic liquids (ILs), i.e. N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEMMA-TFSI), N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium tetrafluoroborate (DEMMA-BF4), N,N,N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide (PP13-TFSI), N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13-TFSI), and N-methyl-N-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P14-TFSI) were investigated by the pulse radiolysis method. The esol− in each of the ammonium ILs has an absorption peak at 1100 nm, with molar absorption coefficients of 1.5–2.3×104 dm3 mol−1 cm−1. The esol− decayed by first order with a rate constant of 1.4–6.4×106 s−1. The reaction rate constant of the solvated electron with pyrene (Py) was 1.5–3.5×108 dm3 mol−1 s−1 in the various ILs. These values were about one order of magnitude higher than the diffusion-controlled limits calculated from measured viscosities. The radiolytic yields (G-value) of the esol− were 0.8–1.7×10−7 mol J−1. The formation rate constant of esol− in DEMMA-TFSI was 3.9×1010 s−1. The dry electron (edry−) in DEMMA-TFSI reacts with Py with a rate constant of 7.9×1011 dm3 mol−1 s−1, three orders of magnitude higher than that of the esol− reactions. The G-value of the esol− in the picosecond time region is 1.2×10−7 mol J−1. The capture of edry− by scavengers was found to be very fast in ILs.