Magnitude of Dynamically Correlated Molecules as an Indicator for a Dynamical Crossover in Ionic Liquids

Musiał, Małgorzata; Cheng, Shinian; Paluch, Marian

doi:10.1021/acs.jpcb.1c00653

Cited by 4 publications

(6 citation statements)

References 38 publications

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“…In the former case, the correlation was empirical and the physical origin underlying the correlation was not clear, but the correlation was useful nonetheless in predicting reaction outcome. A range of other measurements for ionic liquids were considered and for the data presented there is perhaps an interesting correlation with the number of dynamically correlated molecules in the system . A similar order was seen for both nucleofugality and the number of dynamically correlated molecules ( 7 < 2 = 4 < 5 < 6 ) however the origin of any relationship is not clear.…”

Section: Resultsmentioning

confidence: 67%

“…A range of other measurements for ionic liquids were considered and for the data presented there is perhaps an interesting correlation with the number of dynamically correlated molecules in the system. 63 A similar order was seen for both nucleofugality and the number of dynamically correlated molecules (7 < 2 = 4 < 5 < 6) however the origin of any relationship is not clear.…”

Section: -Methylbenzhydryl Chloride 1amentioning

confidence: 99%

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Effects of Ionic Liquids on the Nucleofugality of Chloride

et al. 2021

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The nucleofugality of chloride has been measured in solvent mixtures containing ionic liquids for the first time, allowing reactivity in these solvents to be put in context with molecular solvents. Using well-described electrofuges, solvolysis rate constants were determined in mixtures containing different proportions of ethanol and the ionic liquid 1-butyl-3-methylimidazolium bis-(trifluoromethanesulfonyl)imide; the different solvent effects observed as the mixture changed could be explained using interactions of the ionic liquid with species along the reaction coordinate, determined using temperature dependent kinetic studies. The solvolysis data allowed determination of the nucleofugality of chloride in these mixtures, which varied with the proportion of salt in the reaction mixture, demonstrating quantitatively the importance of the amount of ionic liquid in the reaction mixture in determining reaction outcome. Nucleofugality data for chloride were determined in seven further ionic liquids, with the reactivity shown to vary over more than an order of magnitude. This outcome illustrates that the components of the ionic liquid are critical in determining reaction outcome. Overall, this work quantitatively extends the understanding of solvent effects in ionic liquids and demonstrates the potential for such information to be used to rationally select an ionic liquid to control reaction outcome.

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Section: Resultsmentioning

confidence: 67%

Section: -Methylbenzhydryl Chloride 1amentioning

confidence: 99%

Effects of Ionic Liquids on the Nucleofugality of Chloride

et al. 2021

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“…Therefore, according to standard practice, the empirical Vogel–Fulcher–Tammann (VFT) equation (eq ) has been initially used to parameterize the experimental data σ normald normalc ( T ) = σ 0 exp ( − D T 0 T − T 0 ) where σ 0 denotes the pre-exponential factor, D is the strength parameter characterizing the deviation from Arrhenius behavior, and T 0 denotes the Vogel temperature (sometimes T 0 is also called an ideal glass transition temperature). However, in contrast to other aprotic ILs investigated in the literature, a single VFT function is not enough to describe the dc-conductivity behavior over the entire temperature range. Therefore, two VFT functions have been used to parameterize the 12 decades of σ dc .…”

Section: Resultsmentioning

confidence: 89%

Inflection Point in Pressure Dependence of Ionic Conductivity as a Fingerprint of Local Structure Formation

Koymeth,

Yao,

Paluch

et al. 2024

J. Phys. Chem. B

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In this study, we employed dielectric spectroscopy to investigate the effect of temperature and pressure on the ion dynamics of phosphonium ionic liquids (ILs) differing by the length of an alkyl chain, [P 666,n ][TFSI] (n = 2, 6, 8, 12). We found that both temperature and pressure dependence of dc-conductivity (σ dc ) determined for all examined ILs herein exhibit unique characteristics, unusual for aprotic ILs. Two regions differing by ion self-organization have been identified from the derivative analysis of σ dc (T −1 ) data. On the other hand, isothermal measurements performed at elevated pressure revealed a unique concave−convex character of σ dc (P) dependences, resulting in a clear minimum in the pressure behavior of activation volume. Such an inflection point characterizing the pressure dependence of σ dc in [P 666,n ][TFSI] ILs can be considered an inherent feature of ion dynamics governed by structural self-assembly. Our results offer a unique perspective to link the ion mobility at various T−P conditions to the nanostructural organization of ionic systems.

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“… 8 , 9 For example, incorporating a small chloride anion into the IL structure increases T g . 10 , 11 The same is achieved by introducing strong H-bonding interactions or elongating the alkyl chain in the cation. 12 − 14 However, the latter can also lead to various short-range ordering structures, e.g., clusters or mesoscopic agglomerates, 15 − 17 which might dramatically influence the properties of ILs.…”

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confidence: 99%

“…Under cooling, low-viscosity liquid becomes a supercooled equilibrium fluid that transforms to a nonequilibrium amorphous solid at the glass transition temperature T g . Among the factors controlling the glass-forming ability of ILs, one can mention the symmetry of ionic species, charge delocalization, size of ions, and competing for interionic interactions (van der Waals vs Coulomb forces and H-bonding). , For example, incorporating a small chloride anion into the IL structure increases T g . , The same is achieved by introducing strong H-bonding interactions or elongating the alkyl chain in the cation. − However, the latter can also lead to various short-range ordering structures, e.g., clusters or mesoscopic agglomerates, − which might dramatically influence the properties of ILs. − Therefore, understanding the molecular-level interactions within ILs is crucial for their industrial applications.…”

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confidence: 99%

Tailoring Phosphonium Ionic Liquids for a Liquid–Liquid Phase Transition

Yao

Paluch

Dulski

et al. 2023

J. Phys. Chem. Lett.

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The existence of more than one liquid state in a single-component system remains the most intriguing physical phenomenon. Herein, we explore the effect of cation self-assembly on ion dynamics in the vicinity of liquid−liquid and liquid-glass transition of tetraalkyl phosphonium ([P mmm,n ] + , m = 4, 6; n = 2−14) ionic liquids. We found that nonpolar local domains formed by 14-carbon alkyl chains are crucial in obtaining two supercooled states of different dynamics within a single ionic liquid. Although the nano-ordering, confirmed by Raman spectroscopy, still occurs for shorter alkyl chains (m = 6, n < 14), it does not bring calorimetric evidence of LLT. Instead, it results in peculiar behavior of ion dynamics near the liquid-glass transition and 20-times smaller size of the dynamic heterogeneity compared to imidazolium ionic liquids. These results represent a crucial step toward understanding the nature of the LLT phenomenon and offer insight into the design of efficient electrolytes based on ionic liquids revealing selfassembly behavior.

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Magnitude of Dynamically Correlated Molecules as an Indicator for a Dynamical Crossover in Ionic Liquids

Cited by 4 publications

References 38 publications

Effects of Ionic Liquids on the Nucleofugality of Chloride

Effects of Ionic Liquids on the Nucleofugality of Chloride

Inflection Point in Pressure Dependence of Ionic Conductivity as a Fingerprint of Local Structure Formation

Tailoring Phosphonium Ionic Liquids for a Liquid–Liquid Phase Transition

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