Tuning the melting point of selected ionic liquids through adjustment of the cation's dipole moment

Rabideau, Brooks D.; Soltani, Mohammad; Parker, Rome A.; Siu, Benjamin; Salter, E. Alan; Wierzbicki, Andrzej; Davis, James H.

doi:10.1039/d0cp01214a

Cited by 42 publications

(47 citation statements)

References 40 publications

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“…One should take into consideration not only the increase in the molecular weight of the compound, which is known to increase the melting point, but also the fact that the polar C–I bond creates a molecular dipole, which may favor a better packing of the ions and eventually lead to an increase in the melting point. Recently, Rabideau et al described the possibility of influencing the melting points of ILs through the adjustment of the dipole moment of the cation . Therefore, the strength of the dipole moment, controlled through the incorporation of a halogen into the benzene ring, proves to be a useful tool for influencing this parameter that is often crucial in terms of the application of ILs.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Recently, Rabideau et al described the possibility of influencing the melting points of ILs through the adjustment of the dipole moment of the cation. 36 Therefore, the strength of the dipole moment, controlled through the incorporation of a halogen into the benzene ring, proves to be a useful tool for influencing this parameter that is often crucial in terms of the application of ILs.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Iodosulfuron-Methyl-Based Herbicidal Ionic Liquids Comprising Alkyl Betainate Cation as Novel Active Ingredients with Reduced Environmental Impact and Excellent Efficacy

Niemczak

Sobiech

Grzanka

2020

J. Agric. Food Chem.

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A new family of bio-based herbicidal ionic liquids (HILs) has been synthesized starting from the renewable resource glycine betaine (a derivative of natural amino acids). After esterification, the obtained alkyl betainate bromides containing straight alkyl chains varying from ethyl to octadecyl were combined with a herbicidal anion from the sulfonylurea group (iodosulfuron-methyl). The melting points of the iodosulfuron-methyl-based salts were in a range from 51 to 99 °C, which allows their classification as ionic liquids (ILs). In addition, the new HILs exhibited good affinity for polar and semipolar organic solvents, such as DMSO, methanol, acetonitrile, acetone, and chloroform, while the presence of bulky organic cations reduced their solubility in water. The synthesized products turned out to be stable during storage at 25 °C for over 6 months; however, at 75 °C they underwent fast, progressive degradation and released volatile byproducts. The values of the logarithm of the octanol–water partition coefficient of ILs with alkyls longer than hexyl occurred in the “safe zone” (between 0 and 3); hence, the risk of their migration into groundwater after application or the possibility of their bioaccumulation in the environment is lower in comparison with the currently available commercial form (iodosulfuron-methyl sodium salt). Greenhouse studies confirmed a very high herbicidal efficacy for the obtained salts toward tested plants of oilseed rape, indicating that they may become an attractive replacement for the currently available sulfonylurea-based formulations.

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Section: Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Iodosulfuron-Methyl-Based Herbicidal Ionic Liquids Comprising Alkyl Betainate Cation as Novel Active Ingredients with Reduced Environmental Impact and Excellent Efficacy

Niemczak

Sobiech

Grzanka

2020

J. Agric. Food Chem.

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“…However, a recent study by Rabideau et al. in 2020 showed that the melting points of tetraarylphosphonium salts are inversely correlated to the dipole moment of the cation, which demonstrates that targeted functionalization can be an effective strategy to lower melting points and expand the liquid ranges of the thermally robust salts.…”

Section: Introductionmentioning

confidence: 99%

“…Unfortunately, aryl groups do improve thermal stability of phosphonium salts but at the expense of increasing the melting point, which ultimately reduces the operating window of the ionic liquid. However, a recent study by Rabideau et al in 2020 showed that the melting points of tetraarylphosphonium salts are inversely correlated to the dipole moment of the cation, 29 which demonstrates that targeted functionalization can be an effective strategy to lower melting points and expand the liquid ranges of the thermally robust salts.…”

Section: ■ Introductionmentioning

confidence: 99%

Linking the Thermal and Electronic Properties of Functional Dicationic Salts with Their Molecular Structures

Clarke

Morgan

Hallett

et al. 2021

ACS Sustainable Chem. Eng.

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The two major properties that underpin ionic liquids are tunability and the potential to create task-specific media. Together, these properties allow ionic liquids to surpass the roles long held by traditional molecular solvents. However, at elevated temperatures or under prolonged heating, the structural components that impart such properties decompose or degrade. Dicationic pyridine salts present new opportunities to extend functionality and tunability to high temperatures because they are coordinating and thermally robust. In this work, we present three structurally related series of dicationic pyridine salts, which have been characterized by a wide array of techniques to link thermal and electronic properties to structural variation. The phase transitions and thermal stabilities of the salts were significantly influenced by small structural changes, and several new candidates for high-temperature-based applications were identified. The electron density, and therefore the electron donating ability, of the pyridine functional group could also be controlled by structural variation of cations and anions. Therefore, dicationic pyridine salts are highly tunable choices for task-specific solvents at elevated temperatures. Importantly, thermally robust solvents not only extend operational ranges but also reduce the need to replace or replenish solvents that degrade over time at temperatures commonly employed in industrial settings (i.e., 150−200 °C); solvent lifetimes are extended, and production is reduced. This is a critical requirement for complex media such as ionic liquids, which have high economic and environmental production costs.

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“…Asymmetrical organic cations in combination with either organic or inorganic anions generally destabilize the crystal lattice packing thus favoring the liquid state of the system in terms of enthalpy and entropy. The most intriguing peculiarity of these liquid salts is the possibility to modify their chemical and physical properties (e.g., viscosity, conductivity, hydrophilicity, hydrophobicity, polarity, hydrogen bond forming ability) by an appropriate selection of cation and anion, or by the introduction of specific functional groups in the chemical structure (Branco et al 2011;Rabideau et al 2020). Figure 2a shows some common IL cations and anions.…”

Section: Ionic Liquidsmentioning

confidence: 99%

Cellulose-based fiber spinning processes using ionic liquids

et al. 2022

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Cellulose, a natural, renewable, and environment friendly biopolymer, has been considered as a sustainable feedstock in the near future. However, only 0.3% of cellulose is today processed since it is not soluble in conventional solvents due to the strong hydrogen bonding network and highly ordered structure. Hence, the search of effective and eco-friendly solvents for cellulose dissolution has been a key pillar for decades. In the recent years, ionic liquids (ILs) have been proposed as green solvents for cellulose and have been applied for the production of cellulose-based fibers. This review aims to focus the attention toward fiber spinning methods of cellulose based on ILs, as well as recent progress in cellulose dissolution using ILs. Moreover, the development of cellulosic fibers blended with other biopolymers, and cellulose composites are presented. Finally, different applications of cellulose fibers and composites are summarized and discussed.

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Tuning the melting point of selected ionic liquids through adjustment of the cation's dipole moment

Abstract: Adjusting the dipole moment of an ionic liquid cation through fluorine substitution for hydrogen tunes the melting point.

Cited by 42 publications

References 40 publications

Iodosulfuron-Methyl-Based Herbicidal Ionic Liquids Comprising Alkyl Betainate Cation as Novel Active Ingredients with Reduced Environmental Impact and Excellent Efficacy

Iodosulfuron-Methyl-Based Herbicidal Ionic Liquids Comprising Alkyl Betainate Cation as Novel Active Ingredients with Reduced Environmental Impact and Excellent Efficacy

Linking the Thermal and Electronic Properties of Functional Dicationic Salts with Their Molecular Structures

Cellulose-based fiber spinning processes using ionic liquids

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