Solvatochromic Study on Binary Solvent Mixtures with Ionic Liquids

Koel, Mihkel

doi:10.1515/zna-2008-7-818

Cited by 9 publications

(3 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note, however, that the nonlinearity is substantially reduced when Φ IL is used as the composition variable. Similar composition dependence is observed in UV absorption shifts of the π* probe N , N -dimethyl-4-nitroaniline , in these mixtures, and in the probes phenol blue and Nile Red in the closely related [Im 41 ][PF 6 ] + CH 3 CN system. The departures from linearity in all of these cases might be interpreted as indicating the solute is preferentially solvated by [Im 41 ][BF 4 ].…”

Section: Resultssupporting

confidence: 72%

Solvation Dynamics in a Prototypical Ionic Liquid + Dipolar Aprotic Liquid Mixture: 1-Butyl-3-methylimidazolium Tetrafluoroborate + Acetonitrile

et al. 2014

View full text Add to dashboard Cite

Solvation energies, rotation times, and 100 fs to 20 ns solvation response functions of the solute coumarin 153 (C153) in mixtures of 1-butyl-3-methylimidazolium tetrafluoroborate ([Im41][BF4]) + acetonitrile (CH3CN) at room temperature (20.5 °C) are reported. Available density, shear viscosity, and electrical conductivity data at 25 °C are also collected and parametrized, and new data on refractive indices and component diffusion coefficients presented. Solvation free energies and reorganization energies associated with the S0 ↔ S1 transition of C153 are slightly (≤15%) larger in neat [Im41][BF4] than in CH3CN. No clear evidence for preferential solvation of C153 in these mixtures is found. Composition-dependent diffusion coefficients (D) of Im41(+) and CH3CN as well as C153 rotation times (τ) are approximately related to solution viscosity (η) as D, τ ∝ η(p) with values of p = -0.88, -0.77, and +0.90, respectively. Spectral/solvation response functions (Sν(t)) are bimodal at all compositions, consisting of a subpicosecond fast component followed by a broadly distributed slower component extending over ps-ns times. Integral solvation times (⟨τ(solv)⟩ = ∫(0)(∞)Sν(t) dt) follow a power law on viscosity for mixturecompositions 0.2 ≤ x(IL) ≤ 1 with p = 0.79. With recent broad-band dielectric measurements [J. Phys. Chem. B 2012, 116, 7509] asinput, a simple dielectric continuum model provides predictions for solvation response functions that correctly capture thedistinctive bimodal character of the observed response. At x(IL) ∼ 1 predicted values of ⟨τ(solv)⟩ are smaller than those observed by a factor of 2-3, but the two become approximately equal at x(IL) = 0.2. Predictions of a recent semimolecular theory [J. Phys. Chem. B 2011, 115, 4011] are less accurate, being uniformly slower than the observed solvation dynamics.

show abstract

Section: Resultssupporting

confidence: 72%

Solvation Dynamics in a Prototypical Ionic Liquid + Dipolar Aprotic Liquid Mixture: 1-Butyl-3-methylimidazolium Tetrafluoroborate + Acetonitrile

et al. 2014

View full text Add to dashboard Cite

show abstract

“…Other applications have been found for the pyridinium N -phenolates involving solvent mixtures. Several studies have been carried out on these probes in binary mixtures of molecular solvents with ILs. ,,,− Fletcher and Pandey reported the influence of water on the E T (30) values of [bmim] + [PF 6 ] − , observing that the solvatochromic CT band of dye 1 in the IL is hypsochromically shifted with the addition of water, increasing from E T (30) = 52.4 kcal mol –1 in the IL to 63.1 kcal mol –1 in pure water, corresponding to a Δλ max value of −93 nm (Δν̅ max = +3743 cm –1 ). The ability of the pyridinium N -phenolate dyes to reflect changes in the polarity of ILs in the presence of small amounts of water has been used for analytical purposes, to estimate the water content of ILs using vis spectrophotometric techniques and calibration curves. , An investigation of the polarity of binary mixtures of [bmim] + [PF 6 ] − with TFE using dye 1 revealed that these mixtures are strongly synergistic, an effect that has been referred to as hyperpolarity .…”

Section: Pyridinium N-phenolate Dyes In the Investigation Of Solvent ...mentioning

confidence: 99%

PyridiniumN-Phenolate Betaine Dyes

2014

View full text Add to dashboard Cite

Introduction 10429 2. Historical Contextualization 10431 3. Synthesis of Pyridinium N-Phenolate Dyes 10433 4. Solvatochromic Properties of Pyridinium N-Phenolate Dyes 10435 4.1. X-ray Crystallographic Studies of the Molecular Structures of Pyridinium N-Phenolate Dyes 10437 4.2. Quantum Chemical Calculations Involving Pyridinium N-Phenolate Dyes 10438 4.3. The E T (30) and E T N Solvent Polarity Scale 10440 4.4. Multiparametric Approaches to the Analysis of the E T (30) and E T N Scale 10441 5. Secondary Solvatochromic Pyridinium N-Phenolate Dyes 10442 6. Investigation of the Physical Properties of Room-Temperature Ionic Liquids 10443 7. Thermosolvatochromism of Pyridinium N-Phenolate Dyes 10450 8. Halochromism of Pyridinium N-Phenolate Dyes 10451 9. Piezosolvatochromism of Pyridinium N-Phenolate Dyes 10452 10. Pyridinium N-Phenolate Dyes in the Investigation of Solvent Mixtures 10453 11. Application of Pyridinium N-Phenolate Dyes in the Construction of Chromogenic Chemosensors 10455 11.1. Chirosolvatochromism of Pyridinium N-Phenolate Dyes 10456 11.2. Chromoionophores 10456 11.3. Chromogenic Chemosensors for Anionic Species 10457 11.4. Chromogenic Chemosensors for Neutral Analytes 10458 12. Pyridinium N-Phenolate Dyes as Probes To Measure the Polarity of Solid Surfaces 10459 13. Pyridinium N-Phenolate Dyes in the Study of Microheterogeneous Systems 10460 13.1. Investigation of Surfactants in Aqueous and Organic Media 10462 13.2. Pyridinium N-Phenolate Dyes in the Investigation of Cyclodextrins in Solution 10463 13.

show abstract

“…This nonlinear behavior could explain the occurrence of a minimum in excited-state relaxation time within this range of mixture composition and may be associated with changes in the interactions between the mixture components and the dye at low X IL values. With this respect, various properties of IL-MS mixtures show significant changes in this low X IL region. ,− Indeed, in this range of mole fractions, spectroscopic studies have reported noticeable changes in vibration modes and 1H NMR chemical shifts. Additionally, various chemical and physical properties, such as diffusion and conductivity, exhibit nonlinear changes dependent on the specific IL-MS mixtures.…”

Section: Resultsmentioning

confidence: 99%

Effect of Mixture Composition on the Photophysics of Indoline Dyes in Imidazolium Ionic Liquid-Molecular Solvent Mixtures: A Femtosecond Transient Absorption Study

Maity,

Polok,

Piatkowski

et al. 2024

J. Phys. Chem. B

View full text Add to dashboard Cite

We conducted a study on the photophysics of three indoline dyes, D102, D149, and D205, in binary mixtures of ionic liquids (IL) and polar aprotic molecular solvents (MS). Specifically, we examined the behavior of these dyes in IL-MS mixtures containing four different imidazolium-based ILs and three different polar aprotic MSs. Our investigation involved several techniques, including stationary absorption and emission measurements, as well as femtosecond transient absorption (TA) spectroscopy. Through our analysis, we discovered a peculiar behavior of several photophysical properties at low IL mole fractions (0 < X IL < 0.2). Indeed, in this range of mixture composition, the absorption maximum wavelength decreases noticeably, while the emission maximum wavelength and the Stokes shift, expressed in wavenumbers, reach a maximum. while a minimum occurs in the relative quantum yield and the excited state lifetime. These results indicate that the solvation of dye undergoes a large change in this range of mixture composition. We found that, at high ionic liquid content, the excited relaxation times are correlated with the high viscosity, while at low content, it is the polarity of the solvent that influences the behavior of the excited relaxation times. At a mixture composition of around 0.10, the behavior of the photophysical properties of the studied IL-MS mixtures indicates a crossover between situations where the solvation is dominated by that of ions and that dominated by the solvent.

show abstract

Solvatochromic Study on Binary Solvent Mixtures with Ionic Liquids

Cited by 9 publications

References 26 publications

Solvation Dynamics in a Prototypical Ionic Liquid + Dipolar Aprotic Liquid Mixture: 1-Butyl-3-methylimidazolium Tetrafluoroborate + Acetonitrile

Solvation Dynamics in a Prototypical Ionic Liquid + Dipolar Aprotic Liquid Mixture: 1-Butyl-3-methylimidazolium Tetrafluoroborate + Acetonitrile

PyridiniumN-Phenolate Betaine Dyes

Effect of Mixture Composition on the Photophysics of Indoline Dyes in Imidazolium Ionic Liquid-Molecular Solvent Mixtures: A Femtosecond Transient Absorption Study

Contact Info

Product

Resources

About