Local Structure in Mixtures of Ionic Liquid with Molecular Solvent: Vibration Spectroscopy, NMR and Molecular Dynamics Simulation

Marekha, Bogdan A.; Koverga, Volodymyr; Maity, Nishith; Juhász, A.; Miannay, François-Alexandre; Inkol, Anton; Takamuku, Toshiyuki; Jedlovszky, Pál; Kalugin, Oleg N.; Idriss, Hicham

doi:10.1007/978-981-16-5395-7_10

Cited by 2 publications

(4 citation statements)

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“…The sample temperature was controlled at 298.2 ± 0.1 K by a heater and a dry cold air from a sample cooler (FTS Systems, Air-Jet XR401, TC-84). The digital resolutions of 1 H, 13 C, and 19 F NMR measurements were 4.9 × 10 −4 , 7.6 × 10 −3 , and 3.6 × 10 −3 ppm, respectively. An external double reference tube (Shigemi) was inserted into the sample tube (Shigemi, PS-001-7).…”

Section: Nmr Measurementsmentioning

confidence: 99%

“…An external double reference tube (Shigemi) was inserted into the sample tube (Shigemi, PS-001-7). Hexamethyldisiloxane (Wako Pure Chemicals, the first purity grade) was used as the reference substance for 1 H and 13 C chemical shifts, and trifluoromethylbenzene (Tokyo Chemical Industry, extra grade) was employed as a reference substance for 19 F NMR chemical shifts. The observed chemical shifts were corrected for the volume magnetic susceptibility of a sample solution using an external double reference method.…”

Section: Nmr Measurementsmentioning

confidence: 99%

“…A multiple spectroscopic technique is helpful to understand the molecular-level aspects of IL mixtures from various perspectives. 10,13 For example, the situation of a specific nuclei can be elucidated by NMR. 14−17 Observations of the unique intramolecular vibrational modes (typically over 800 cm −1 ) by IR and Raman spectroscopies reveal the specific interactions of functional groups in the targets.…”

Section: Introductionmentioning

confidence: 99%

“…A multiple spectroscopic technique is helpful to understand the molecular-level aspects of IL mixtures from various perspectives. , For example, the situation of a specific nuclei can be elucidated by NMR. − Observations of the unique intramolecular vibrational modes (typically over 800 cm –1 ) by IR and Raman spectroscopies reveal the specific interactions of functional groups in the targets. − The intermolecular vibrational band that appears in the low-frequency region below 200 cm –1 can be detected by femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) − and terahertz time-domain spectroscopy, , which are complementary spectroscopic methods to observe Raman- and IR-active motions in the low-frequency region and probe the microscopic intermolecular interaction and structure in liquids − including ILs. − The direct measurement of intermolecular vibrational spectra is significant because the intermolecular interactions affecting the liquid properties of ILs and their mixtures must be determined to tune these liquid properties . Frequency-domain Raman and far-IR spectroscopies have also been applied for several ILs. ,, Intermolecular vibrations are often treated as fluctuations in liquids and solutions from a dynamical aspect.…”

Section: Introductionmentioning

confidence: 99%

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Exploring the Microscopic Aspects of 1-Methyl-3-octylimidazolium Tetrafluoroborate Mixtures with Formamide, N-Methylformamide, and N,N-Dimethylformamide by Multiple Spectroscopic Techniques and Computations

et al. 2023

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The microscopic aspects of 1-methyl-3-octylimidazolium tetrafluoroborate ([MOIm][BF 4 ]) mixtures with formamide (FA), N-methylformamide (NMF), and N,N-dimethylformamide (DMF) were investigated using spectroscopic techniques of femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES), FT-IR, and NMR. Molecular dynamics simulations and quantum chemistry calculations were also performed. According to fs-RIKES, the first moment of the low-frequency spectrum bands mainly originating from the intermolecular vibrations in the [MOIm]-[BF 4 ]/FA and [MOIm][BF 4 ]/DMF systems changed gradually with the molecular liquid mole fraction X ML but that in the [MOIm][BF 4 ]/NMF system was constant up to X NMF = 0.7 and then gradually increased in the range of X NMF ≥ 0.7. Excluding the contribution of the 2D hydrogen-bonding network due to the presence of FA in the low-frequency spectrum band, the X ML dependence of the normalized first moment of the low-frequency band in the [MOIm][BF 4 ]/FA and [MOIm][BF 4 ]/NMF systems revealed that the normalized first moment did not remarkably change in the range of X ML < 0.7 but drastically increased in X ML ≥ 0.7. FT-IR results indicated that the amide C�O band shifted to the lowfrequency side with increasing X ML for the three mixtures due to the hydrogen bonds. The imidazolium ring C−H band also showed a similar tendency to the amide C�O band. 19 F NMR probed the microenvironment of [BF 4 ] − in the mixtures. The [MOIm][BF 4 ]/NMF and [MOIm][BF 4 ]/DMF systems showed an up-field shift of the F atoms of the anion with increasing X ML , and the [MOIm][BF 4 ]/FA system exhibited a down-field shift. Steep changes in the chemical shifts were confirmed in the region of X ML > 0.8. On the basis of the quantum chemistry calculations, the observed chemical shifts with increasing X ML were mainly attributed to the many-body interactions of ions and amides for the [MOIm][BF 4 ]/FA and [MOIm][BF 4 ]/DMF systems. Meanwhile, the long distance between the cation and the anion was due to the high dielectric medium for the [MOIm][BF 4 ]/NMF system, which led to an up-field shift.

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Section: Nmr Measurementsmentioning

confidence: 99%

Section: Nmr Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%