N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts : Ionic liquid properties and plastic crystal behaviour

A series of N-methyl-N-alkylpyrrolidinium nonafluoro-1-butanesulfonate salts were synthesised and characterised. The thermophysical characteristics of this family of salts have been investigated with respect to potential use as ionic liquids and solid electrolytes. N-Methyl-N-butylpyrrolidinium nonafluoro-1-butanesulfonate (p_1,4NfO) has the lowest melting point of the family, at 94 °C. Electrochemical analysis of p_1,4 NfO in the liquid state shows an electrochemical window of ~6 V. All compounds exhibit one or more solid–solid transitions at sub-ambient temperatures, indicating the existence of plastic crystal phases.

Methanesulfonate and p-toluenesulfonate salts of the N-methyl-N-alkylpyrrolidinium and quaternary ammonium cations : novel low cost ionic liquids

The preparation and characterization of a series of novel salts, based on the N-methyl-N-alkylpyrrolidinium or quaternary ammonium organic cations coupled with sulfonate type anions, namely the mesylate (CH₃SO₃⁻) and tosylate (CH₃C₆H₄SO₃⁻) anions are reported. These salts are analogues of the previously described organic cation bis(trifluoromethanesulfonyl)amide (TFSA) salts that form useful ionic liquids of interest in “Green” synthesis. Several of the salts are liquid below 50 °C, e.g. tributylhexylammonium tosylate and ethylmethylpyrrolidinium mesylate and one is liquid at and below room temperature (tributylhexylammonium mesylate). These new salts have a cost advantage over salts of the TFSA⁻, PF₆⁻ and CF₃SO₃⁻ anions. Electrochemical and thermal properties have been investigated. The salts are stable to beyond 100 °C and exhibit electrochemical potential windows of at least ±2 V vs. Ag/Ag+. Some of the salts exhibit multiple crystalline phases below their melting points, potentially indicative of plastic crystal behaviour, whilst others showed more simple solid–liquid behaviour. Many of the salts were found to be glass forming.

N-methyl-N-alkylpyrrolidinium hexafluorophosphate salts : novel molten salts and plastic crystal phases

A new series of salts, based on the N-methyl-N-alkylpyrrolidinium cation and the PF₆- anion, are reported and their thermal properties described for alkyl = Me, Et, Pr, Bu, Hx, and Hp. X-ray structures of several of the salts are also reported. The N,N-dimethylpyrrolidinium hexafluorophosphate has a melting point greater than 390 °C; however, the N-methyl-N-butylpyrrolidinium derivative melts at 70 °C. Most of the PF₆- salts were observed to have lower melting points in comparison with the analogous iodide salts. Most of the salts exhibit one or more thermal transitions prior to melting and a final entropy of melting less than 20 J K^-1 mol^-1, behavior which has previously been associated with the formation of plastic crystal phases. Good crystal structure solutions were obtained at low temperatures in the case of the alkyl = propyl and heptyl derivatives. The loss of diffraction peaks and changes in symmetry at higher temperatures indicated the presence of dynamic rotational disorder, supporting the understanding that the plastic properties arise from rotational motions in the crystal.

Weak intermolecular interactions in sulfonamide salts : structure of 1-ethyl-2-methyl-3-benzyl imidazolium bis[(trifluoromethyl)sulfonyl]amide

The crystal structure of a 1,2,3-trisubstituted imidazolium salt of the bis[(trifluoromethyl)sulfonyl)]amide ion is presented; this salt is a prototype for similar, room temperature liquid, imidazolium salts; the structure shows that the anion and cation interact weakly, with little if any hydrogen bonding present.

Microstructural and molecular level characterisation of plastic crystal phases of pyrrolidinium trifluoromethanesulfonyl salts

Ambient temperature conductive plastic crystal phases of alkylmethylpyrrolidinium trifluoromethanesulfonyl amide (TFSA) salts are studied using positron annihilation lifetime spectroscopy (PALS) to examine the role of vacancy size and concentration in conductivity. The ethyl methylpyrrolidinium TFSA salt (P₁₂ TFSA) has larger vacancies and a greater concentration of vacancies than the dimethylpyrrolidinium TFSA salt (P₁₁ TFSA) over the temperature range investigated. The relative vacancy size and concentration vary with temperature and reflect the solid–solid transitions as measured by differential scanning calorimetry (DSC). P₁₂ TFSA has greater conductivity than P₁₁ TFSA and has furthermore been observed to exhibit slip planes at room temperature. P₁₂ TFSA has greater entropy changes associated with solid–solid phase transitions below the melting point than P₁₁ TFSA possibly indicating greater rotational freedom in P₁₂ TFSA. These results support the notion that the diffusion, conduction, and plastic flow properties of the pyrrolidinium TFSA salts are derived from the lattice vacancies.

N-methyl-N-alkylpyrrolidinium bis(perfluoroethylsulfonyl)amide ([NPf2]–) and tris(trifluoromethanesulfonyl)methide ([CTf3]–) salts : synthesis and characterization

Novel salts based the pyrrolidinium cation [C_nmpyr]⁺ (where n denote the number of carbons in the straight alkyl chain) and either the [NPf₂]^– or [CTf₃]^– anions have been synthesized and characterized to determine their thermal behaviour, stability, and conductivity. [C₁mpyr][NPf₂], [C₂mpyr][NPf₂], and [C₁mpyr][CTf₃] exhibit behaviour indicative of a plastic crystal phase. Both [C₃mpyr][NPf₂] and [C₄mpyr][NPf₂] are RTILs, while all of the [CTf₃]^– salts, have melting points above 60°C. [C₃mpyr][NPf₂] exhibited the widest electrochemical window of 5.5 V. The [NPf2]– salt exhibited similar reductive limits to the [NTf₂]^– anion, –3.2 V versus Fc⁺|Fc, while [CTf₃]^– had lower reductive stability. The [CTf₃]^– salts were more stable towards oxidation, +2.5 V versus Fc⁺|Fc, compared to the [NPf₂]^– and [NTf₂]^– salts.

Low viscosity ionic liquids based on organic salts of the dicyanamide anion

New families of salts viz. quaternary ammonium, N-alkyl-N-methylpyrrolidinium or 1-alkyl-3-methylimidazolium dicyanamides, Cat⁺N(CN)₂⁻, are low melting compounds, most being liquid at rt, water-miscible and have low (for ionic liquids) viscosity at rt, e.g.η = 21 cP for 1-ethyl-3-methylimidazolium dicyanamide.

Pyrrolidinium imides : a new family of molten salts and conductive plastic crystal phases

A new family of molten salts is reported, based on the N-alkyl, N-alkyl pyrrolidinium cation and the bis(trifluoromethane sulfonyl)imide anion. Some of the members of the family are molten at room temperature, while the smaller and more symmetrical members have melting points around 100 °C. Of the room-temperature molten salt examples, the methyl butyl derivative exhibits the highest conductivity; at 2 × 10^-3 S/cm this is the highest molten salt conductivity observed to date at room temperature among the ammonium salts. This highly conductive behavior is rationalized in terms of the role of cation planarity. The salts also exhibit multiple crystalline phase behavior below their melting points and exhibit significant conductivity in at least their higher temperature crystal phase. For example, the methyl propyl derivative (mp = 12 °C) shows ion conductivity of 1 × 10^-6 S/cm at 0 °C in its higher temperature crystalline phase.

High conductivity molten salts based on the imide ion

The bis(trifluoromethanesulfonyl)imide ion has recently been used in its lithium salt as a useful ion in solid polymer electrolytes because of the reduced degree of ion interaction its diffuse charge generates. In this work we have synthesised a number of novel salts based on the ammonium and pyrrolidinium cations of this anion. The salts all show reduced melting points compared with analogous halide salts. In some cases they are molten at room temperature. This latter group of salts have been characterized with respect to their properties as ionic liquids; the highest room temperature conductivity 2 mS cm⁻¹ being exhibited by methyl butyl pyrrolidinium imide. Many of the salts are glass forming, exhibiting glass transition temperatures in the region of −90°C.

Physical trends and structural features in organic salts of the thiocyanate anion

A new series of ionic liquids based on the thiocyanate anion has been prepared. Incorporation of this anion with an imidazolium, tetraalkylammonium or pyrrolidinium cation produces ionic liquids with advantageously low melting points and good thermal stability. The low temperature phase behaviour of the salts has been investigated using differential scanning calorimetry and multiple solid phases have been observed. The electrochemical windows of representative imidazolium and pyrrolidinium species have been investigated by cyclic voltammetry and determined to be 2.4 and 3.5 V, respectively. In addition, the solid-state structure of N,N-dimethylpyrrolidinium thiocyanate has been determined by X-ray crystallography. This is the first reported structure of a pyrrolidinium thiocyanate species and shows a layered structure with linear thiocyanate groups having bond lengths comparable to those observed in similar SCN−-containing species.

Room-temperature molten salts based on the quaternary ammonium ion

The properties of a family of novel quaternary ammonium salts based on the bis(trifluoromethylsulfonyl)imide and triflate anions are reported. Binary phase diagrams for some of their mixtures and their electrochemical windows of stability are also reported. The highest conductivity observed in the pure salt systems at 25 °C was 7 × 10^-4 S cm^-1. An electrochemical window of stability of up to 5 V was measured on graphite electrodes. The effect of salt structure and solvent on conductivity of the salts is also discussed.

Synthesis and properties of ambient temperature molten salts based on the quaternary ammonium ion

The synthesis of 16 tetraalkyl ammonium bis(trifluoromethane sulfonyl) imide salts, (C_nH_2n+1)₄ +N -N (SO₂CF₃)₂ (n = 1, 2, 3, 4),  (C₂H₅)₂(i-C₃H₇)₂ +N -N(SO₂CF₃)₂, (C₂H₅)(CH₃)(i-C₃H₇)₂+N-N(SO₂CF₃)₂, (n-C₇H₁₅)(C₂H₅)i-C₃H₇)₂+N-N(SO₂CF₃)₂ and (C_nH_2n+1)(C_mH_2m+1)₃+N-N(SO₂CF₃)₂ (n = 6,7,8; m = 1, 2, 4) are reported in this paper. Trends in properties of these salts are discussed. The symmetrical tetraalkyl ammonium salts with the bis(trifluoromethyl sulfonyl) imide anion exhibited a lower melting point than that of corresponding ammonium halides. The salts with low symmetry ammonium cations were found to be of generally lower melting point, and many were stable liquids at room temperature. Several of these did not crystallize during cooling below room temperature and exhibited glass transition temperatures in the region of −60 °C∼−80 °C. A comparison of properties between the ammonium imide salts and corresponding trifluoromethane sulfonates is also presented.

Conductive plastic crystal phases of the 1-alkyl-2-methyl pyrrolinium TFSA salts

Characterization of a new family of salts, based on a number of 1-alkyl-2-methyl pyrrolinium cations and the bis(trifluoromethane sulfonyl) amide anion (TFSA), is presented. From the thermal analysis, conductivity and X-ray diffraction (XRD) measurements, at least one of the compounds of the family, 1-ethyl-2-methyl pyrrolinium TFSA, was found to exhibit plastic crystal phases before melting and to exhibit high conductivity in the solid state (1×10⁻⁴ S cm⁻¹ at 25 °C). This plastic crystal behaviour is discussed in comparison with other members of this pyrrolinium salt family.

Nonadditivity of faradaic currents and modification of double layer capacitance in the voltammetry of mixtures of ferrocene and ferrocenium salts in ionic liquids

Electrochemical studies on the Fc + e− Fc+ (Fc = ferrocene) process have been undertaken via the oxidation of Fc and reduction of Fc+ as the hexafluorophosphate (PF6−) or tetrafluoroborate (BF4−) salts and their mixtures in three ionic liquids (ILs) (1-butyl-1-methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-butyl-3-methylimidazolium hexafluorophosphate). Data obtained at macro- and microdisk electrodes using conventional dc and Fourier-transformed large-amplitude ac (FT-ac) voltammetry reveal that diffusion coefficients for Fc and Fc+ differ significantly and are a function of the Fc and Fc+ concentration, in contrast to findings in molecular solvents with 0.1 M added supporting electrolyte media. Thus, the Faradaic currents associated with the oxidation of Fc (Fc0/+) and reduction of FcPF6 or FcBF4 (Fc+/0) when both Fc and Fc+ are simultaneously present in the ILs differ from values obtained when individual Fc and Fc+ solutions are used. The voltammetry for both the Fc0/+ and Fc+/0 processes exhibited near-Nernstian behavior at a glassy carbon macrodisk electrode and a platinum microdisk electrode, when each process was studied individually in the ILs. As expected, the reversible formal potentials (E°′) and diffusion coefficients (D) at 23 ± 1 °C were independent of the electrode material and concentration. However, when Fc and FcPF6 or FcBF4 were both present, alterations to the mass transport process occurred and apparent D values calculated for Fc and Fc+ were found to be about 25−39% and 32−42% larger, respectively, than those determined from individual solutions. The apparent value of the double layer capacitance determined by FT-ac voltammetry from individual and mixed Fc and Fc+ conditions at the GC electrode was also a function of concentration. Double layer capacitance values increased significantly with the concentration of Fc and FcPF6 or FcBF4 when species were studied individually or simultaneously, but had a larger magnitude under conditions where both species were present. Variation in the structure of the ILs and hence mobilities of the ionic species, when Fc and FcPF6 or FcBF4 are simultaneously present, is considered to be the origin of the nonadditivity of the Faradaic currents and variation in capacitance.