Interrogating the mechanism of the solvation dynamics in BmimBF4/PC mixtures: A cooperative study employing time-resolved fluorescence and molecular dynamics

Smortsova, Yevheniia; Miannay, François-Alexandre; Gustavsson, T.; Sauvage, Frédéric; Ingrosso, Francesca; Kalugin, Oleg N.; Idrissi, A.

doi:10.1016/j.molliq.2021.117163

Cited by 3 publications

(8 citation statements)

References 88 publications

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“…Here, we note that this slow solvation dynamics lasting hundreds of picoseconds was also previously reported for D149 in [C 2 mim][N(CN) 2 ] (red- shift of SE in TA spectra) and for C153 in BmimBF 4 /BmimTFSI-PC , (red shift of time-resolved emission spectrum), while femtosecond optical Kerr effect (OKE) measurements revealed a similar time scale for bulk IL relaxation. − …”

Section: Resultssupporting

confidence: 82%

“…Here, we note that this slow solvation dynamics lasting hundreds of picoseconds was also previously reported for D149 in [C 2 mim][N(CN) 2 ] 100 (red-shift of SE in TA spectra) and for C153 in BmimBF 4 /BmimTFSI-PC 101,102 (red shift of time-resolved emission spectrum), while femtosecond optical Kerr effect (OKE) measurements revealed a similar time scale for bulk IL relaxation. 103−107 In addition, to our best knowledge, TA spectra were previously reported for only two of our dyes, i.e., D149, 30 D102 in ACN, 33 and D149 in an equimolar mixture of ACN and t-Butanol (t-BuOH).…”

Section: Maxsupporting

confidence: 84%

“…Lastly, τ 4 can be attributed to the decay process of the charge transfer (CT) excited state. Furthermore, considering the presence of very slow solvation dynamics time components (especially in pure ILs and at higher X IL mixtures) found in previous studies, , we cannot discount the possibility of the solvation process contributing to both τ 3 and τ 4 as well.…”

Section: Resultsmentioning

confidence: 76%

“…However, in essence, all of the global analysis time components can be viewed as mixed-time components, incorporating multiple excited state processes. For instance, both τ 1 and τ 2 may involve solvation dynamics ,,− alongside intramolecular vibrational relaxation (IVR), dye aggregation, and the ultrafast decay of the locally excited (LE)/Franck–Condon state, while τ 3 may primarily involve excited state vibrational relaxation and ultrafast twisting. Lastly, τ 4 can be attributed to the decay process of the charge transfer (CT) excited state.…”

Section: Resultsmentioning

confidence: 99%

“…Composition dependence of τ 1 / τ 1 X IL = 1 ((A),(C),(E)) and τ 2 / τ 2 X IL = 1 (B,D,F) in case of D102 (A),B), D149 (C,D), and D205 (E,F) in all studied IL-MS mixtures. (G) Composition dependence of previously published ,,− average solvation time (normalized as τ solv / τ solv X IL = 1 ) in the case of similar types of IL-MS mixtures. For better comprehension of the composition dependence, we have normalized each data point by the highest value within its respective series, which corresponds to the values at X IL = 1.…”

Section: Resultsmentioning

confidence: 99%

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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

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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.

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