Molecular design principles of ionic liquids with a sulfonyl fluoride moiety

Siegel, David J.; Anderson, Grace I.; Cyr, Noah; Lambrecht, Daniel S.; Zeller, Mat­thias; Hillesheim, Patrick C.; Mirjafari, Arsalan

doi:10.1039/d0nj05603k

Cited by 13 publications

(15 citation statements)

References 59 publications

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“…Changing from an imidazolium to a pyridinium cation generally raises T g /T m and, as expected, it was found that a protic amino group pendant on the pyridinium cation brings about a dramatic increase in T m . 34 We note that hydrogen bonding is not singularly responsible for 9 and 10 having higher T m values than 1 and 2, but rather the observed ΔT m likely reflects a net effect accounting also for the impact of increased cation symmetry. Following on previous studies evaluating the impact of the dipole on physicochemical properties of the ILs, we performed quantum chemical simulations in order to evaluate the electronic environment associated with the different substitutions on the rings.…”

Section: Structure−physicochemical Property Relationshipsmentioning

confidence: 72%

Anticancer Agents as Design Archetypes: Insights into the Structure–Property Relationships of Ionic Liquids with a Triarylmethyl Moiety

et al. 2022

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A fundamental challenge underlying the design principles of ionic liquids (ILs) entails a lack of understanding into how tailored properties arise from the molecular framework of the constituent ions. Herein, we present detailed analyses of novel functional ILs containing a triarylmethyl (trityl) motif. Combining an empirically driven molecular design, thermophysical analysis, X-ray crystallography, and computational modeling, we achieved an in-depth understanding of structure–property relationships, establishing a coherent correlation with distinct trends between the thermophysical properties and functional diversity of the compound library. We observe a coherent relationship between melting (T m) and glass transition (T g) temperatures and the location and type of chemical modification of the cation. Furthermore, there is an inverse correlation between the simulated dipole moment and the T m/T g of the salts. Specifically, chlorination of the ILs both reduces and reorients the dipole moment, a key property controlling intermolecular interactions, thus allowing for control over T m/T g values. The observed trends are particularly apparent when comparing the phase transitions and dipole moments, allowing for the development of predictive models. Ultimately, trends in structural features and characterized properties align with established studies in physicochemical relationships for ILs, underpinning the formation and stability of these new lipophilic, low-melting salts.

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Section: Structure−physicochemical Property Relationshipsmentioning

confidence: 72%

Anticancer Agents as Design Archetypes: Insights into the Structure–Property Relationships of Ionic Liquids with a Triarylmethyl Moiety

et al. 2022

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“…We previously noted that strategically placed side-chain branching poses a substantial depressive effect on the melting point ( T m ) values of ILs in which they are incorporated. − Encouraged by these results, we speculated that using a mixture of hydrophobic amino acids as the basis for our anions might provide a workable degree of fluidity (viz. reducing melting point and viscosity) on the part of the IL, thus improving the efficiency of the resulting salts to chemisorb CO 2 from air.…”

Section: Introductionmentioning

confidence: 94%

Direct Air Capture of CO₂ via Ionic Liquids Derived from “Waste” Amino Acids

Recker

Green

Soltani

et al. 2022

ACS Sustainable Chem. Eng.

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Direct capture of CO 2 from anthropogenic emissions is an imperative societal task as the concentration of global atmospheric CO 2 continues to increase drastically. The longterm goal of negative emission requires methods to remove carbon directly from the atmosphere, oceanwater, and nonpoint sources. Ionic liquids (ILs) have had a pivotal impact on finding and implementing innovative solutions that enable a more sustainable future. Here, we report the first example of an IL-enabled approach for direct CO 2 capture from the atmosphere on a laboratory scale. These de novo bioderived materials represent an ideal milieu for direct carbon capture applications because of their nonvolatility and a priori low toxicity. Easily prepared liquid salts based on a mixture of three common amino acids, valine, leucine, and isoleucine, were found to be effective sorbents for ready and reversible CO 2 sequestration from air despite its very low concentration. Collectively known as branched-chain amino acid, they are commonly derived from biowaste products, for example, feathers, fur, and even human hair. Therefore, the resultant ILs from the "waste" amino acids provide an exciting prospect in terms of CO 2 transformation and waste utilization. We provided valuable design insights for engineering structure−property relationships in amino acid-based ILs. The impact of moisture on the absorption characteristics and capacity was evaluated in ambient conditions. We postulate that the high capture efficiency and stability of these ILs make them superior to present amine-and alkali-assisted approaches for the direct air capture of CO 2 as a scalable process.

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“…Furthermore, 4-(2aminoethyl)benzenesulfonyl fluoride (AEBSF) hydrochloride was reported to improve the crystallisation quality and phase stability of formamidinium lead iodide (FAPbI3) perovskite, which is used in solar cells, thus increasing the power conversion efficiency of the FAPbI3-based photovoltaic 162 . In 2021, Hillesheim and Mirjafari reported a series of sulfonyl fluoride-containing task-specific ionic liquids (ILs), which demonstrated good thermodynamic stability against hydrolysis and thermolysis, and could be prepared in multigram scale with minimal purification 163 . Given the established biocompatibility of sulfonyl fluorides, the preparation of ILs of this type which also incorporate components of active pharmaceutical ingredients are expected to find biological applications.…”

Section: Sufex In Materials Chemistrymentioning

confidence: 99%

Sulfonyl fluorides as targets and substrates in the development of new synthetic methods

Lou

Willis²

2022

Nat Rev Chem

169

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The advent of sulfur(VI)-fluoride exchange (SuFEx) processes as transformations with click-like reactivity has invigorated research into electrophilic species featuring a sulfur-fluorine bond. Amongst these, sulfonyl fluorides have emerged as the work-horse functional group, with diverse applications being reported. Sulfonyl fluorides are used as electrophilic warheads by both medicinal chemists and chemical biologists. The balance of reactivity and stability that is so attractive for these applications, particularly the resistance of sulfonyl fluorides to hydrolysis under physiological conditions, has provided opportunities for synthetic chemists. New synthetic approaches that start with sulfur-containing substrates include the activation of sulfonamides using pyrilium salts, the deoxygenation of sulfonic acids, and the electrochemical oxidation of thiols. Employing non-sulfur containing substrates has led to the development of transition-metal-catalysed processes based on palladium, copper and nickel, as well as the use of SO2F2 gas as an electrophilic hub. Selectively manipulating molecules that already contain a sulfonyl fluoride group has also proven to be a popular tactic, with metal-catalysed processes again at the fore. Finally, coaxing sulfonyl fluorides to engage with nucleophiles, when required, and under suitable reaction conditions, has led to new activation methods. This review provides an overview of the challenges in the efficient synthesis and manipulation of these intriguing functional groups.

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Molecular design principles of ionic liquids with a sulfonyl fluoride moiety

Abstract: New family of SO2F-functionalized ionic liquids.

Cited by 13 publications

References 59 publications

Anticancer Agents as Design Archetypes: Insights into the Structure–Property Relationships of Ionic Liquids with a Triarylmethyl Moiety

Anticancer Agents as Design Archetypes: Insights into the Structure–Property Relationships of Ionic Liquids with a Triarylmethyl Moiety

Direct Air Capture of CO₂ via Ionic Liquids Derived from “Waste” Amino Acids

Sulfonyl fluorides as targets and substrates in the development of new synthetic methods

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Molecular design principles of ionic liquids with a sulfonyl fluoride moiety

Abstract: New family of SO2F-functionalized ionic liquids.

Cited by 13 publications

References 59 publications

Anticancer Agents as Design Archetypes: Insights into the Structure–Property Relationships of Ionic Liquids with a Triarylmethyl Moiety

Anticancer Agents as Design Archetypes: Insights into the Structure–Property Relationships of Ionic Liquids with a Triarylmethyl Moiety

Direct Air Capture of CO2 via Ionic Liquids Derived from “Waste” Amino Acids

Sulfonyl fluorides as targets and substrates in the development of new synthetic methods

Contact Info

Product

Resources

About

Direct Air Capture of CO₂ via Ionic Liquids Derived from “Waste” Amino Acids