Reactions of solvated electrons with imidazolium cations in ionic liquids

Takahashi, Kenji; Sato, Toru; Katsumura, Yosuke; Yang, Jinfeng; Kondoh, Takafumi; Yoshida, Yasuhiko; Katoh, Ryuzi

doi:10.1016/j.radphyschem.2008.05.042

Cited by 55 publications

(48 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The reaction constants of three C2-alkyl imidazolium cations [1-ethyl-2,3-dimethylimdazolium, 1-butyl-2,3-dimethylimdazolium (BMMI + ), 1-hexyl-2,3-dimethylimdazolium] with hydrated electrons were examined, and were found to be very close each other, 5.9×10 9 , 5.5×10 9 , and 5.1×10 9 L mol −1 s −1 , respectively, whereas that of the BMI + cation was 1.8×10 10 L mol −1 s −1 . These findings are quite similar to those of Takahashi et al [19]. They found that alkylation of the imidazolium suppresses reactivity with dry electrons.…”

Section: Reactions With Hydrated Electronssupporting

confidence: 92%

Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

Zhang

Cao

et al. 2012

Chin. Sci. Bull.

View full text Add to dashboard Cite

The reactions of imidazolium-based ionic liquids having different substituent groups on the ring with hydrated electrons (e − aq ), hydroxyl radicals (  OH), and sulfate anion radicals (SO 4 − ) were investigated using nanosecond pulse radiolysis techniques. The spectra of these ionic liquids on reaction with e aq − all exhibited a similar peak at about 320 nm, and a typical peak for e − aq in aqueous ionic liquid solutions. The reaction rate constants for 1,3-disubstituted imidazolium-based ionic liquid hexafluorophosphates (BMIPF 6 ) with e aq − were deduced to be 10 10 L mol −1 s −1 , however the values were lower for trisubstituted ionic liquids. For example, the rate constant for 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (BMMIBF 4 ) was 5.5×10 9 L mol −1 s −1 . Imidazolium-based ionic liquids reacted with hydroxyl radicals via adducts to produce a mixture of isomeric OH adducts, and the pk a value of the OH adducts was deduced to be 8.4±0.4 for 1-butyl-3-methylimdazolium tetrafluoroborate (BMIBF 4 ). Moreover, imidazolium cations were also oxidized by SO 4 − to produce bivalent cation radicals, which exhibit a peak at 320 nm, and these rate constants are of the same order of magnitude, i.e., 10 9 L mol −1 s −1 , except that for 1-(2-hydroxyethyl)-3-methylimdazolium tetrafluoroborate with SO 4 − (k=2.8×10 8 L mol −1 s −1 ). Theoretical calculations were carried out to estimate the structures of the products of reduction by e aq − and the results were related to the experimental data.pulse radiolysis, imidazolium-based ionic liquids, kinetics, rate constants Citation:Fu H Y, Xing Z G, Cao X Y, et al. Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids.

show abstract

Section: Reactions With Hydrated Electronssupporting

confidence: 92%

Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

Zhang

Cao

et al. 2012

Chin. Sci. Bull.

View full text Add to dashboard Cite

show abstract

“…Several pulse radiolysis studies on ionic liquids (Behar et al, 2001;Behar et al, 2002;Grodkowski and Neta, 2002a-c;Wishart and Neta, 2003;Grodkowski et al, 2003;Wishart et al, 2005;Kato, et al, 2007;Takahashi et al, 2007;Kimura et al, 2007) have been reported. The researches indicate that, for the imidazolium ionic liquids, dry electrons produced by ionization before full solvation are rapidly scavenged by the solvent molecules.…”

Section: Introductionmentioning

confidence: 99%

Molar absorption coefficient and radiolytic yield of solvated electrons in diethylmethyl(2-methoxy)ammonium bis (trifluoromethanesulfonyl)imide ionic liquid

Asano

Yang

Kondoh

et al. 2008

Radiation Physics and Chemistry

Self Cite

View full text Add to dashboard Cite

The molar absorption coefficient and the radiolytic yield of solvated electron in ionic liquid of DEMMA-TFSI were estimated respectively to be 2.3 × 10 4 L mol -1 cm -1 and 0.8 × 10 -7 mol J -1 by observing the reaction and kinetics of solvated electron and dry electron in the ionic liquid. The solvated electron in DEMMA-TFSI has a very broad absorption spectrum peaking at 1100 nm and reacts slowly with pyrene with a rate constant of 3.5 × 10 8 L mol -1 s -1 , while the dry electron is captured rapidly by pyrene with C 37 value of 0.065 mol L -1 .

show abstract

“…The chemical reactivity in ionic liquids has been begun to be studied. Several nanosecond pulse radiolysis studies of ionic liquids (Behar et al, 2001(Behar et al, , 2002Grodkowski and Neta, 2002a-c;Wishart and Neta, 2003;Grodkowski et al, 2003;Katoh et al, 2007;Asano et al, 2007;Takahashi et al, 2007;Kimura et al, 2007) and picosecond studies (Wishart et al, 2005) have been published. The researches indicate that, for the imidazolium ionic liquids, the electrons produced by ionization are rapidly scavenged by the solvent molecules before they become fully solvated, while the electrons in the ammonium ionic liquids are solvated quickly to form the solvated electrons.…”

Section: Picosecond Dynamics Of Solvated Electrons In Ionic Liquidmentioning

confidence: 99%

Picosecond pulse radiolysis: Dynamics of solvated electrons in ionic liquid and geminate ion recombination in liquid alkanes

Yang

Kondoh

Norizawa

et al. 2008

Radiation Physics and Chemistry

Self Cite

View full text Add to dashboard Cite

A picosecond pulse radiolysis facility based on a laser-driven photocathode electron accelerator has been constructed. First observation of picosecond dynamics in ionic liquid of DEMMA-TFSI in radiation chemistry was reported. It is found that the electrons produced by ionization are solvated to full solvation in ionic liquid with a rate constant of 3.9 × 10 10 s -1 , and dry electrons before full solvation react rapidly with biphenyl and pyrene with rate constant of 3.8 to 7.9 × 10 11 dm 3 mol -1 s -1 . The geminate ion recombination in n-dodecane and n-hexane was also observed by monitoring transient optical absorption at 523 nm.

show abstract

Reactions of solvated electrons with imidazolium cations in ionic liquids

Cited by 55 publications

References 18 publications

Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

Pulse radiolysis studies of functionally substituted imidazolium-based ionic liquids

Molar absorption coefficient and radiolytic yield of solvated electrons in diethylmethyl(2-methoxy)ammonium bis (trifluoromethanesulfonyl)imide ionic liquid

Picosecond pulse radiolysis: Dynamics of solvated electrons in ionic liquid and geminate ion recombination in liquid alkanes

Contact Info

Product

Resources

About