Design of Deep Eutectic Systems: Plastic Crystalline Materials as Constituents

Alhadid, Ahmad; Nasrallah, Sahar; Mokrushina, Liudmila; Minceva, Mirjana

doi:10.3390/molecules27196210

Cited by 4 publications

(3 citation statements)

References 58 publications

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“…Our findings for ChCl serve as a foundation for the development of DESs centred around ionic plastic crystals. We propose to prepare liquids from ionic plastic crystals that simultaneously profit from (1) a low Δ fus H m 30 and (2) favourable mixing of the ionic and molecular compounds balancing intermolecular interactions and disorder 31 . Both aspects can be tuned by selecting the appropriate ions and molecular compounds and significantly increase the melting point depression of the salt, yielding dense ionic fluids at accessible temperatures over a broad range of compositions.…”

Section: Resultsmentioning

confidence: 99%

Defying decomposition: the curious case of choline chloride

van den Bruinhorst,

Avila,

Rosenthal

et al. 2023

Nat Commun

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Chemists aim to meet modern sustainability, health, and safety requirements by replacing conventional solvents with deep eutectic solvents (DESs). Through large melting point depressions, DESs may incorporate renewable solids in task-specific liquids. Yet, DES design is complicated by complex molecular interactions and a lack of comprehensive property databases. Even measuring pure component melting properties can be challenging, due to decomposition before melting. Here we overcame the decomposition of the quintessential DES constituent, choline chloride (ChCl). We measured its enthalpy of fusion (13.8 ± 3.0 kJ ⋅ mol) and melting point (687 ± 9 K) by fast scanning calorimetry combined with micro-XRD and high-speed optical microscopy. Our thermodynamically coherent fusion properties identify ChCl as an ionic plastic crystal and demonstrate negative deviations from ideal mixing for ChCl—contradicting previous assumptions. We hypothesise that the plastic crystal nature of ammonium salts governs their resilience to melting; pure or mixed. We show that DESs based on ionic plastic crystals can profit from (1) a low enthalpy of fusion and (2) favourable mixing. Both depress the melting point and can be altered through ion selection. Ionic plastic crystal-based DESs thus offer a platform for task-specific liquids at a broad range of temperatures and compositions.

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Section: Resultsmentioning

confidence: 99%

Defying decomposition: the curious case of choline chloride

van den Bruinhorst,

Avila,

Rosenthal

et al. 2023

Nat Commun

View full text Add to dashboard Cite

show abstract

“…[8] Our findings for ChCl serve as a foundation for the development of DESs centred around ionic plastic crystals. These mixtures simultaneously profit from a low ∆ fus H m [31] and strong deviations from ideal eutectic behaviour, yielding liquids at accessible temperatures over a broad range of compositions. Ionic plastic crystal based DESs thus provide a platform to include solids with a low environmental or safety impact in a renewable liquid solvent with task-specific properties.…”

Section: Hqgrmentioning

confidence: 99%

Defying Decomposition: The Curious Case of Choline Chloride

Bruinhorst

Ávila

Rosenthal

et al. 2023

Preprint

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Chemists are exploring deep eutectic solvents (DESs) as alternatives to conventional solvents to meet modern sustainability, health, and safety requirements.[1–3] DESs incorporate renewable solids in task-specific liquids through large melting point depressions.[3] Yet, DES design is complicated by complex molecular interactions and a lack of comprehensive and reliable property databases.[3–6] Even measuring the melting properties of pure DES components can be challenging, as they often decompose before melting.[7–9] Here we overcame the decomposition of a quintessential DES constituent, choline chloride (ChCl). We measured its enthalpy of fusion (13.8 ± 3.0 kJ·mol−1) and melting point (687±9 K) by fast scanning calorimetry (FSC) combined with micro-XRD and high-speed optical microscopy. Our thermodynamically coherent fusion properties identify ChCl as an ionic plastic crystal[10] and demonstrate negative deviations from ideal mixing for ChCl— contradicting the conclusions based on previously assumed fusion properties.[5,7,11] We hypothesise that the plastic crystal nature of ammonium salts is at the basis of their resilience to melting when pure or mixed with other components. Our results thus pave the way for ionic plastic crystal-based DESs, liquid at accessible temperatures and over a broad range of compositions.

show abstract

“…[8] Our findings for ChCl serve as a foundation for the development of DESs centred around ionic plastic crystals. We propose to prepare liquids from ionic plastic crystals that simultaneously profit from (1) a low ∆ fus H m [32] and (2) favourable mixing of the ionic and molecular compounds balancing intermolecular interactions and disorder [4] . Both aspects can be tuned by selecting the appropriate ions and molecular compounds and significantly increase the melting point depression of the salt, yielding dense ionic fluids at accessible temperatures over a broad range of compositions.…”

Section: Hqgrmentioning

confidence: 99%

Defying Decomposition: The Curious Case of Choline Chloride

Bruinhorst

Ávila

Rosenthal

et al. 2023

Preprint

View full text Add to dashboard Cite

Chemists are exploring deep eutectic solvents (DESs) as alternatives to conventional solvents to meet modern sustainability, health, and safety requirements.[1–3] Through large melting point depressions, DESs allow for the incorporation of renewable solids in taskspecific liquids.[3] Yet, DES design is complicated by complex molecular interactions and a lack of comprehensive and reliable property databases.[3–6] Even measuring the melting properties of pure DES components can be challenging, as they often decompose before melting.[7–9] Here we overcame the decomposition of the quintessential DES constituent, choline chloride (ChCl). We measured its enthalpy of fusion (13.8 ± 3.0 kJ·mol−1) and melting point (687 ± 9 K) by fast scanning calorimetry (FSC) combined with micro-XRD and high-speed optical microscopy. Our thermodynamically coherent fusion properties identify ChCl as an ionic plastic crystal[ 10,11] and demonstrate negative deviations from ideal mixing for ChCl—contradicting the conclusions based on previously assumed fusion properties.[5,7,12] We hypothesise that the plastic crystal nature of ammonium salts is at the basis of their resilience to melting when pure or mixed with other components. We show that DESs based on ionic plastic crystals can profit from (1) a low enthalpy of fusion and (2) favourable mixing of the ionic and molecular compounds. Both lower the mixture’s melting point and can be altered through the nature of the ions. Ionic plastic crystal-based DESs thus offer a platform for task-specific liquids at accessible temperatures and over a broad range of compositions.

show abstract

Design of Deep Eutectic Systems: Plastic Crystalline Materials as Constituents

Cited by 4 publications

References 58 publications

Defying decomposition: the curious case of choline chloride

Defying decomposition: the curious case of choline chloride

Defying Decomposition: The Curious Case of Choline Chloride

Defying Decomposition: The Curious Case of Choline Chloride

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