Protic ionic liquids as recyclable solvents for the acid catalysed synthesis of diphenylmethyl thioethers

Henderson, Luke C.; Thornton, Megan; Byrne, Nolene; Fox, Bronwyn; Waugh, Kelsey D.; Squire, Jennifer S.; Servinis, Linden; Delaney, Joshua P.; Brozinski, Hannah L.; Andrighetto, Luke M.; Altimari, Jarrad M.

doi:10.1016/j.crci.2013.04.002

Cited by 11 publications

(7 citation statements)

References 49 publications

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“…The conversion of aliphatic, aromatic, and heterocyclic thiols into diphenylmethyl thioethers was conducted in the nonstoichiometric PIL of triethylammonium methanesulfonate, with 10% excess methane sulfuric acid. High yields of 63–99% were achieved in short times, with the solvent able to be recycled …”

Section: Catalysis and Organic Synthesismentioning

confidence: 99%

Protic Ionic Liquids: Evolving Structure–Property Relationships and Expanding Applications

2015

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Section: Catalysis and Organic Synthesismentioning

confidence: 99%

Protic Ionic Liquids: Evolving Structure–Property Relationships and Expanding Applications

2015

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“…Not only does the presence of the conjugate acid/base pair lead to minimal energy losses between the oxidation and reduction reactions in a range of electrochemical devices, ,,,, but it also gives the ability to tune the potentials of those reactions through the choice of p K a . , For instance, the p K a of aromatic heterocyclic cations can be chosen within a wide range of values with appropriate substitution pattern, , prompting several investigations into nonstoichiometric protic ionic liquids with azole bases including imidazole − and triazole . Nonstoichiometric protic ionic liquids have found use not only in electrochemical applications but also in a broad range of other fields including catalysis, , gel formation, and pharmaceutical formulations. , While there have been several studies of azoles immobilized in polymeric structures, − ,− only very few have explored acid doping in less than stoichiometric amounts, producing nonstoichiometric equivalents of protic poly(ionic liquids). ,, …”

Section: Introductionmentioning

confidence: 99%

Highly Conductive Nonstoichiometric Protic Poly(ionic liquid) Electrolytes

Karlsson

Jannasch

2019

ACS Appl. Energy Mater.

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Nonstoichiometric protic ionic liquids have recently gained interest because proton acceptors are crucial in the electrolyte of many electrochemical applications such as fuel cells, proton batteries, and supercapacitors. In the present work we have prepared and studied several protic poly(ionic liquids) doped with acid in nonstoichiometric amounts. The poly(ionic liquids) were based on poly(dimethylsiloxane) backbones functionalized with imidazole, 1,2,4-triazole and benzimidazole groups, respectively, via flexible alkyl spacer units. These polymers did not show any observable glass transition above −50 °C, resulting in high charge mobility and conductivities of up to 19 μS/cm at 25 °C. Additional doping with free imidazole significantly increased the conductivity, to 0.15 mS/cm at 25 °C, more than 4 orders of magnitude higher than in the nondoped state. The origins of the fast charge transport in these polymer electrolytes were investigated by electrochemical impedance spectroscopy and electrode polarization analysis. The results indicate that these kinds of nonstoichiometric protic poly(ionic liquids) have potential as high-performance electrolytes for room-temperature electrochemical cells, such as organic proton batteries, where the availability of both proton donors and acceptors is important.

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“…Furthermore, the benefits of nonstoichiometric protic ionic liquid electrolytes are now increasingly discussed for a broader range of protic electrochemical devices. ,− For example, it has recently been shown that stoichiometric protic ionic liquids cannot be efficiently used as fuel cell electrolytes, and that proton shuttles in the form of the conjugate organic base are needed . Nonstoichiometric protic ionic liquids have also yielded superior performance as electrolytes in carbon supercapacitors , as well as in a range of other fields including catalysis, , gel formation, and pharmaceutical formulations. , …”

Section: Introductionmentioning

confidence: 99%

“…2,6−9 For example, it has recently been shown that stoichiometric protic ionic liquids cannot be efficiently used as fuel cell electrolytes, and that proton shuttles in the form of the conjugate organic base are needed. 6 Nonstoichiometric protic ionic liquids have also yielded superior performance as electrolytes in carbon supercapacitors 1,7 as well as in a range of other fields including catalysis, 10,11 gel formation, 12 and pharmaceutical formulations. 1,13 In a seminal work by Angell et al, the importance of ΔpK a on the stability, ionicity, and conductivity of protic ionic liquids is detailed.…”

Section: ■ Introductionmentioning

confidence: 99%

Charge Transport in Nonstoichiometric 2-Fluoropyridinium Triflate Protic Ionic Liquids

et al. 2019

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Pyridinium triflates are highly dissociated protic ionic liquids, and nonstoichiometric compositions have been used in protic energy devices such as the all-organic proton battery. Herein, we use a combination of pulsed field gradient NMR spectroscopy and electrochemical impedance spectroscopy to investigate the charge transport properties of the nonstoichiometric protic ionic liquid 2-fluoropyridinium triflate and the variation with the acid-doping level. While all diffusion coefficients decreased with the level of acid doping, the room-temperature conductivity increased because of the concurrent increase in charge carrier concentration. The maximum room-temperature conductivity was 7.33 mS/cm, obtained when 14% of the pyridine was protonated with triflic acid, while higher acid-doping levels lead to liquid/solid mixtures with low conductivity. PEDOT supercapacitor cells with this electrolyte demonstrated very high capacitance (83.9 F/g) and charge storage capacity (23.3 mA h/g). In addition, we predict that using an acid-doping level lower than before will result in superior electrolyte performance in proton batteries because of improvements in conductivity, processability, and electrochemical stability.

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Protic ionic liquids as recyclable solvents for the acid catalysed synthesis of diphenylmethyl thioethers

Cited by 11 publications

References 49 publications

Protic Ionic Liquids: Evolving Structure–Property Relationships and Expanding Applications

Protic Ionic Liquids: Evolving Structure–Property Relationships and Expanding Applications

Highly Conductive Nonstoichiometric Protic Poly(ionic liquid) Electrolytes

Charge Transport in Nonstoichiometric 2-Fluoropyridinium Triflate Protic Ionic Liquids

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