Dynamics of Fast Reactions in Ionic Liquids

Funston, Alison M.; Wishart, James F.

doi:10.1021/bk-2005-0901.ch008

Cited by 29 publications

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“…The substitution of alkyl groups in cations with their homologous ether groups in side groups of cations generally changes the physical properties of ILs. ,− In particular, the melting point, glass-transition temperature, and viscosity of ILs are lowered by replacing the alkyl chain with the corresponding ether group. This can be ascribed to the flexibility of the ether group compared to the corresponding alkyl group.…”

Section: Discussionmentioning

confidence: 99%

“…Generally, the ether substitution of alkyl groups in cations significantly affects the physical properties, including fragility. ,− For example, [N 222(2O2O2) ][NTf 2 ] and [P 222(2O2O2) ]-[NTf 2 ] are more fragile than the corresponding [N 2228 ][NTf 2 ] and [P 2228 ][NTf 2 ] . Thus, the ether substitution tends to render the ILs more fragile.…”

Section: Discussionmentioning

confidence: 99%

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Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Pyrrolidinium-Based Ionic Liquids: Effects of Anion Species

Kakinuma

Shirota

2019

J. Phys. Chem. B

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We investigated the temperature dependence of the intermolecular vibrational dynamics of pyrrolidinium-based ionic liquids (ILs) with 10 different anion species using femtosecond Raman-induced Kerr effect spectroscopy. The features of the temperature-dependent vibrational spectra vary with the different anions. In the case of the ILs with spherical top anions, such as tetrafluoroborate and hexafluorophosphate, and trifluoromethanesulfonate, the spectral intensity in the low-frequency region below 50 cm–1 increases with rising temperature, while that in the high-frequency region above 50 cm–1 remains almost unchanged. Similar temperature-dependent features were also found in the bis(fluorosulfonyl)amide and bis(perfluoroalkylsulfonyl)amide salts. However, the difference spectra at respective temperature relative to 293 K indicate that the spectra of the bis(fluorosulfonyl)amide and bis(perfluoroalkylsulfonyl)amide salts are more temperature-sensitive in the low-frequency region below 50 cm–1 compared to those of the tetrafluoroborate, hexafluorophosphate, and trifluoromethanesulfonate salts. The spectra of 1-butyl-1-methylpyrrolidinium-based ILs with dicyanamide and tricyanomethide anions show a characteristic temperature dependence; in addition to an increase of the spectral intensity in the low-frequency region below 50 cm–1, a red shift of the spectra in the high-frequency side above 50 cm–1 was observed with increasing temperature. This implies that the librational motions of planar dicyanamide and tricyanomethide anions contribute substantially to the low-frequency spectra. We also compared the temperature-dependent low-frequency spectra of 1-butyl-1-methylpyrrolidinium- and 1-(2-methoxyethyl)-1-methylpyrrolidinium-based ILs with some anions. Although the spectral shapes are slightly different in the range of 70–150 cm–1, which can be attributed to the intramolecular vibrational modes of the cations, the temperature dependence of the spectral shapes is quite similar, indicating that the ether substitution in the cation side groups has little effects on the temperature dependence of the low-frequency spectra. The fragilities of the ILs were also estimated from the temperature-dependent viscosities and the glass-transition temperatures. The fragility parameter seems to be correlated with the temperature dependence of the first moment of the low-frequency spectral bands mainly arising from the intermolecular vibrations of the ILs.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Pyrrolidinium-Based Ionic Liquids: Effects of Anion Species

Kakinuma

Shirota

2019

J. Phys. Chem. B

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“…For example, several research groups demonstrated reduced viscosities and melting points for ILs by substituting ether groups in the place of alkyl groups on both aromatic and nonaromatic cations. [16][17][18][19] Dyson and co-workers showed that a substantial viscosity reduction can be achieved for imidazolium ILs by replacing an alkyl group with a nitrile group. 20 In a previous study, we prepared new Si-substituted imidazolium ILs.…”

Section: Introductionmentioning

confidence: 99%

Intermolecular Interactions and Dynamics of Room Temperature Ionic Liquids That Have Silyl- and Siloxy-Substituted Imidazolium Cations

2007

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The intermolecular interactions and dynamics of novel ionic liquids with alkylsilyl and alkylsiloxy substitutions on the cations are studied by measuring the intermolecular vibrational spectra and reorientational dynamics using femtosecond Kerr effect methods. The new ionic liquids include 1-dimethylphenylsilylmethyl-3-methylimidazolium (PhSi-mim+), and 1-methyl-3-pentamethyldisiloxymethylimidazolium (SiOSi-mim+) cations paired with the bis(trifluoromethylsulfonyl)imide (NTf(2)-) anion. Measured ionic liquid viscosities are surprisingly low for such bulky cation substituents. DFT electronic structure calculations on the isolated ions provide additional information about the electrostatic interactions.

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“…The particular reactivities of various classes of anions and cations will also be examined. To save space, some aspects of ionic liquid radiation chemistry are included here by reference to previous reviews. − …”

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confidence: 99%

“…To save space, some aspects of ionic liquid radiation chemistry are included here by reference to previous reviews. [15][16][17][18][19] It is useful to organize the major processes that occur in irradiated ionic liquids according to the schemes shown in the Table of Contents graphic at the top of the article and in Figure 1 (while acknowledging that the schemes are not comprehensive and other processes occur as well). Referring first to the graphic above, deposition of energy from the incident radiation to the medium (in this case an ionic liquid) generates a range of excited states (IL*) and ionizations that eject electrons from the ions of the ionic liquid, leaving behind electron vacancies ("holes").…”

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confidence: 99%

Ionic Liquids and Ionizing Radiation: Reactivity of Highly Energetic Species

Wishart

2010

J. Phys. Chem. Lett.

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Due to their unique properties, ionic liquids present many opportunities for basic research on the interactions of radiation with materials under conditions not previously available. At the same time, there are practical applied reasons for characterizing, understanding, and being able to predict how ionicliquid-based devices and industrial-scale systems will perform under conditions of extreme reactivity, including radiation. This perspective discusses current issues in ionic liquid physical chemistry, provides a brief introduction to radiation chemistry, draws attention to some key findings in ionic liquid radiation chemistry, and identifies some current hot topics and new opportunities.

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Dynamics of Fast Reactions in Ionic Liquids

Cited by 29 publications

References 0 publications

Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Pyrrolidinium-Based Ionic Liquids: Effects of Anion Species

Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Pyrrolidinium-Based Ionic Liquids: Effects of Anion Species

Intermolecular Interactions and Dynamics of Room Temperature Ionic Liquids That Have Silyl- and Siloxy-Substituted Imidazolium Cations

Ionic Liquids and Ionizing Radiation: Reactivity of Highly Energetic Species

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