A Computational and Spectroscopic Analysis of Solvate Ionic Liquids Containing Anions with Long and Short Perfluorinated Alkyl Chains.

Anion-driven, nanoscale polar-apolar structural organization is investigated in a solvate ionic liquid (SIL) setting by comparing sulfonate-based anions with long and short perfluorinated alkyl chains. Representative SILs are created from 1,2-bis(2-methoxyethoxy)ethane ("triglyme" or "G3"), lithium nonafluoro-1-butanesulfonate, and lithium trifluoromethanesulfonate. Molecular dynamics simulations, density functional theory computations, and vibrational spectroscopy provide insight into the overall liquid structure, cation-solvent interactions, and cation-anion association. Significant competition between G3 and anions for cation-binding sites characterizes the G3-LiC4F9SO3 mixtures. Only 50% of coordinating G3 molecules form tetradentate complexes with Li+ in [(G3)1Li][C4F9SO3]. Moreover, the SIL is characterized by extensive amounts of ion pairing. Based on these observations, [(G3)1Li][C4F9SO3] is classified as a "poor" SIL, similar to the analogous [(G3)1Li][CF3SO3] system. Even though the comparable basicity of the CF3SO3- and C4F9SO3- anions leads to similar SIL classifications, the hydrophobic fluorobutyl groups support extensive apolar domain formation. These apolar moieties permeate throughout [(G3)1Li][C4F9SO3] and persist even at relatively low dilution ratios of [(G3)10Li][C4F9SO3]. By way of comparison, the CF3 group is far too short to sustain polar-apolar segregation. This demonstrates how chemically modifying the anions to include hydrophobic groups can impart unique nanoscale organization to a SIL. Moreover, tuning these nano-segregated fluorinated domains could, in principle, control the presence of dimensionally ordered states in these mixtures without changing the coordination of the lithium ions.

Confinement Effects on the Magnetic Ionic Liquid 1-Ethyl-3-methylimidazolium Tetrachloroferrate(III).

Confinement effects for the magnetoresponsive ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate(III), [C2mim]FeCl4, are explored from thermal, spectroscopic, and magnetic points of view. Placing the ionic liquid inside SBA-15 mesoporous silica produces a significant impact on the material's response to temperature, pressure, and magnetic fields. Isobaric thermal experiments show melting point reductions that depend on the pore diameter of the mesopores. The confinement-induced reductions in phase transition temperature follow the Gibbs-Thomson equation if a 1.60 nm non-freezable interfacial layer is postulated to exist along the pore wall. Isothermal pressure-dependent infrared spectroscopy reveals a similar modification to phase transition pressures, with the confined ionic liquid requiring higher pressures to trigger phase transformation than the unconfined system. Confinement also impedes ion transport as activation energies are elevated when the ionic liquid is placed inside the mesopores. Finally, the antiferromagnetic ordering that characterizes unconfined [C2mim]FeCl4 is suppressed when the ionic liquid is confined in 5.39-nm pores. Thus, confinement provides another avenue for manipulating the magnetic properties of this compound.

The Effect of Fluorinated Solvents on the Physicochemical Properties, Ionic Association, and Free Volume of a Prototypical Solvate Ionic Liquid.

Solvate ionic liquid (SIL) synthesis and properties depend on a delicate balancing of cation-solvent and cation-anion interactions to produce materials containing only cation-solvent complexes and solvent-separated anions. Most SILs meeting these characteristics fall within the paradigm of oligomeric ethylene oxides (e.g. glymes and glycols) and lithium salts. Targeted functionalization of solvent molecules to achieve desired properties is a relatively unexplored avenue of research. Fluorinated solvents have significantly different electric charge distributions compared to their nonfluorinated analogs. We test the impact of solvent fluorination for a SIL created from equimolar mixtures of lithium bis(trifluoromethylsulfonyl)imide (LiNTf2 ) and triethylene glycol (TEG), hereafter [(TEG)1 Li]NTf2 . In the first experiment, TEG is partially substituted with 2,2,4,4,5,5,7,7-octafluoro-3,6-dioxaoctane-1,8-diol (FTEG). This leads to a precipitous decrease in ionic conductivity and larger quantities of ionically-associated Li(NTf2 )2 - species, as detected with vibrational spectroscopy. These observations suggest FTEG does not readily coordinate Li+ ions in a manner analogous to TEG. Computational studies reinforce this conclusion. Relative complex cation stabilities are ranked as [(FTEG)1 Li]+ >[(TEG)1 Li]+ . A second experiment adds FTEG as a diluent to [(TEG)1 Li]NTf2 . This places FTEG and TEG in competition to coordinate a limited number of Li+ ions. The resulting mixtures exhibit conductivity enhancement over the parent SIL and minimal changes in ion speciation due to the poor Li+ binding by FTEG compared to TEG. Positron annihilation lifetime spectroscopic studies point to increased amounts of free volume upon dilution of FTEG. This likely explains the origin of the conductivity and viscosity enhancements.

Erratum: 2,2,3,3,4,4,5,5-Octa-fluorohexa-ne-1,6-diol. -Corrigendum.

[This corrects the article DOI: 10.1107/S2414314620004459.].

Quantitative Investigation of Ion Clusters in a Double Salt Ionic Liquid by Both Vibrational Spectroscopy and Molecular Dynamics Simulation.

Vibrational spectroscopy and molecular dynamics simulations are powerful tools frequently used to elucidate interactions among ions in ionic liquid electrolyte solutions. We apply these techniques to characterize ionic interactions in mixtures of 1-butyl-1-methylpyrrolidinium trifluoromethansulfonate, [C1C4pyr][CF3SO3], and lithium trifluoromethanesulfonate, LiCF3SO3, namely, [Li]0.091[C1C4pyr]0.909[CF3SO3] and [Li]0.167[C1C4pyr]0.833[CF3SO3]. The computational and experimental data indicate that extensive, LiCF3SO3-rich regions exist within the solutions, and most of the anionic species that are composed of these domains are either [Li2CF3SO3]+ or LiCF3SO3 moieties. The [Li]0.167[C1C4pyr]0.833[CF3SO3] system contains a larger number of [Li2CF3SO3]+ and [Li3CF3SO3]2+ species than [Li]0.091[C1C4pyr]0.909[CF3SO3], which may explain, in part, the reduction in ionic conductivity when LiCF3SO3 is added to [C1C4pyr][CF3SO3]. The charge-organized liquid structure inherent to [C1C4pyr][CF3SO3] supports the dynamic coupling of vibrationally induced dipole moments to form optical phonons. Consequently, intense, IR-active vibrational modes are split into transverse optical and longitudinal optical components. Band splitting is reduced when LiCF3SO3 is added to the ionic liquid, suggesting that ionically associated anions impede the ability of the ionic liquid to support optical phonons.

2,2,3,3,4,4,5,5-Octa-fluorohexa-ne-1,6-diol.

In the crystal of the title compound, C6H6F8O4, O-H⋯O hydrogen bonds involving the hy-droxy groups connect the mol-ecules, forming a two-dimensional network parallel to (100). These hydrogen-bonding inter-actions appear to drive the O-C-C-O torsion angles into a gauche-trans-trans series of conformations along the backbone of the mol-ecule.

Dipolar coupling and molecular vibrations in ionic liquids.

It is often the case that intense, non-degenerate bands appear asymmetric in transmission IR spectra of ionic liquids, with a high-frequency shoulder adjacent to the dominant band. Moreover, the band shape is temperature dependent with lower temperatures producing greater amounts of asymmetry. The 1-alkyl-3-methylimidazolium trifluoromethanesulfonate family of ionic liquids provides an excellent illustration of this phenomenon, wherein the νs(SO3) mode of the anion is split into two components whose frequencies change with temperature. In this article, a new theoretical model is derived to explain temperature-dependent trends in the infrared spectra of these materials. According to the model, vibrationally-induced dipole moments couple with one another across the charge-organized liquid structure inherent to ionic liquids to produce transverse optical (TO) and longitudinal optical (LO) phonons. The temperature dependence of the resulting TO-LO band splitting originates from two distinct sources. First, the interaction strength between vibrationally-induced dipole moments depends on the distance separating the ions, which in turn, is directly related to the ionic liquid's density. Second, TO-LO splitting requires a significant amount of angular correlation among the ions to facilitate the propagation of optical phonons. Elevated temperatures produce smaller densities and increased amounts of disorder, both of which lead to decreased amounts of TO-LO splitting. Although the model is developed in the context of ionic liquids, the equations are broadly applicable to other materials that possess long-range structure but are not fully crystalline, such as molten salts, plastic crystalline compounds, glasses, and disordered solids.

The Nature of Cation-Anion Interactions in Magnetic Ionic Liquids as Revealed Using High-Pressure Fourier Transform Infrared (FT-IR) Spectroscopy.

Magnetic ionic liquids are a group of magneto-responsive compounds that typically possess high ionic conductivities and low vapor pressures. In spite of the general interest in these materials, a number of questions concerning the fundamental interactions among the ions remain unanswered. We used vibrational spectroscopy to gain insight into the nature of these interactions. Intramolecular vibrational modes of the ions are quite sensitive to their local potential energy environments, which are ultimately defined by cation-anion coordination schemes present among the ions. Ambient pressure Fourier transform infrared (FT-IR) spectroscopy indicates comparable interaction motifs for 1-ethyl-3-methylimidazolium tetrachloroferrate(III), [emim]FeCl4, and 1-ethyl-3-methylimidazolium tetrabromoferrate(III), [emim]FeBr4, magnetic ionic liquids. However, the vibrational modes of [emim]FeCl4 generally occur at slightly higher frequencies than those of [emim]FeBr4. These differences reflect different interaction strengths between the [emim]+ cations and FeCl4- or FeBr4- anions. This conclusion is supported by gas-phase ab initio calculations of single [emim]FeCl4 and [emim]FeBr4 ion pairs that show longer C-H···Br-Fe interaction lengths compared to C-H···Cl-Fe. Although the IR spectra of [emim]FeCl4 and [emim]FeBr4 are comparable at ambient pressure, a different series of spectroscopic changes transpire when pressure is applied to these compounds. This suggests [emim]+ cations experience different types of interaction with the anions under high-pressure conditions. The pressure-dependent FT-IR spectra highlights the critical role ligands attached to the tetrahalogenoferrate(III) anions play in modulating cation-anion interactions in magnetic ionic liquids.

Temperature- and pressure-dependent infrared spectroscopy of 1-butyl-3-methylimidazolium trifluoromethanesulfonate: A dipolar coupling theory analysis.

Continued growth and development of ionic liquids requires a thorough understanding of how cation and anion molecular structure defines the liquid structure of the materials as well as the various properties that make them technologically useful. Infrared spectroscopy is frequently used to assess molecular-level interactions among the cations and anions of ionic liquids because the intramolecular vibrational modes of the ions are sensitive to the local potential energy environments in which they reside. Thus, different interaction modes among the ions may lead to different spectroscopic signatures in the vibrational spectra. Charge organization present in ionic liquids, such as 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4mim]CF3SO3), is frequently modeled in terms of a quasicrystalline structure. Highly structured quasilattices enable the dynamic coupling of vibrationally-induced dipole moments to produce optical dispersion and transverse optical-longitudinal optical (TO-LO) splitting of vibrational modes of the ionic liquid. According to dipolar coupling theory, the degree of TO-LO splitting is predicted to have a linear dependence on the number density of the ionic liquid. Both temperature and pressure will affect the number density of the ionic liquid and, therefore, the amount of TO-LO splitting for this mode. Therefore, we test these relationships through temperature- and pressure-dependent FT-IR spectroscopic studies of [C4mim]CF3SO3, focusing on the totally symmetric SO stretching mode for the anion, νs(SO3). Increased temperature decreases the amount of TO-LO splitting for νs(SO3), whereas elevated pressure is found to increase the amount of band splitting. In both cases, the experimental observations follow the general predictions of dipolar coupling theory, thereby supporting the quasilattice model for this ionic liquid.

Liquid Structure of Bis(trifluoromethylsulfonyl)imide-Based Ionic Liquids Assessed by FT-IR Spectroscopy.

Ionic liquids are a fertile and active area of research, in part, due to the unique properties these solvents offer over traditional molecular solvents. Because these properties are rooted in the fundamental ion-ion interactions that govern their liquid structure, there is a strong motivation to characterize the liquid structure of ionic liquids. Infrared spectroscopy is a standard analytical tool for assessing liquid structures, for the intramolecular vibrational modes of the ions composing the materials are often quite sensitive to their local potential energy environment. In this work, we demonstrate that the band asymmetry for the νa(SNS) anion mode of N(Tf)2--based ionic liquids originates from the dynamic coupling of vibrationally induced dipole moments of anions across a quasilattice. The magnitude of TO-LO splitting is linearly correlated with the number densities of the ionic liquids; an observation that is in accord with the predictions of dipolar coupling theory. Dipole moment derivatives of νa(SNS) calculated from dipolar coupling theory, (∂µ/∂q)DCT, are lower than those obtained from independent measurements of (∂µ/∂q). The most likely explanation for this disparity is that although ionic liquids possess sufficient long-range structure to support TO-LO splitting of infrared-active modes, there is enough orientational and translational disorder in the quasilattice to partially disrupt the coupling of vibrationally induced dipole moments across the quasilattice. This will result in diminished amounts of TO-LO splitting than would be expected if the ionic liquid were a perfect crystal at 0 K. Impacts of cation molecular structure and the formation of a binary solution on the liquid structure are also explored.

Mass and charge transport in 1-alkyl-3-methylimidazolium triflate ionic liquids.

Temperature-dependent transport properties in ionic liquids, such as the ionic conductivity and fluidity, are often characterized empirically through equations that require multiple adjustable fitting parameters in order to adequately describe the data. These fitting parameters offer no insight into the molecular-level mechanism of transport. Here the temperature dependence of these transport properties in 1-alkyl-3-methylimidazolium triflate ionic liquids is explained using the compensated Arrhenius formalism (CAF), where the conductivity or fluidity assumes an Arrhenius-like form that also contains a dipole density dependence in the exponential prefactor. The resulting CAF activation energies for conductivity and fluidity are much higher than those obtained from polar organic liquids and electrolytes. The CAF very accurately describes the temperature dependence of both conductivity and fluidity using only system properties (i.e., density and activation energy). These results imply that the transport mechanism in molten salts is very similar to that in polar organic liquids and electrolytes.

Using FT-IR spectroscopy to measure charge organization in ionic liquids.

A major goal in the field of ionic liquids is correlating transport property trends with the underlying liquid structure of the compounds, such as the degree of charge organization among the constituent ions. Traditional techniques for experimentally assessing charge organization are specialized and not readily available for routine measurements. This represents a significant roadblock in elucidating these correlations. We use a combination of transmission and polarized-ATR infrared spectroscopy to measure the degree of charge organization for ionic liquids. The technique is illustrated with a family of 1-alkyl-3-methylimidazolium trifluoromethanesulfonate ionic liquids at 30 °C. As expected, the amount of charge organization decreases as the alkyl side chain is lengthened, highlighting the important role of short-range repulsive interactions in defining quasilattice structure. Inherent limitations of the method are identified and discussed. The quantitative measurements of charge organization are then correlated with trends in the transport properties of the compounds to highlight the relationship between charge and momentum transport and the underlying liquid structure. Most research laboratories possess infrared spectrometers capable of conducting these measurements; thus, the proposed method may represent a cost-effective solution for routinely measuring charge organization in ionic liquids.

Polymer chain organization in tensile-stretched poly(ethylene oxide)-based polymer electrolytes.

Polymer chain orientation in tensile-stretched poly(ethylene oxide)-lithium trifluoromethanesulfonate polymer electrolytes are investigated with polarized infrared spectroscopy as a function of the degree of strain and salt composition (ether oxygen atom to lithium ion ratios of 20:1, 15:1, and 10:1). The 1359 and 1352 cm(-1) bands are used to probe the crystalline PEO and P(EO)(3)LiCF(3)SO(3) domains, respectively, allowing a direct comparison of chain orientation for the two phases. Two-dimensional correlation FT-IR spectroscopy indicates that the two crystalline domains align at the same rate as the polymer electrolytes are stretched. Quantitative measurements of polymer chain orientation obtained through dichroic infrared spectroscopy show that chain orientation predominantly occurs between strain values of 150% and 250%, regardless of salt composition investigated. There are few changes in chain orientation for either phase when the films are further elongated to a strain of 300%; however, the PEO domains are slightly more oriented at the high strain values. The spectroscopic data are consistent with stretching-induced melt-recrystallization of the unoriented crystalline domains in the solution-cast polymer films. Stretching the films pulls polymer chains from the crystalline domains, which subsequently recrystallize with the polymer helices parallel to the stretch direction. If lithium ion conduction in crystalline polymer electrolytes is viewed as consisting of two major components (facile intra-chain lithium ion conduction and slow helix-to-helix inter-grain hopping), then alignment of the polymer helices will affect the ion conduction pathways for these materials by reducing the number of inter-grain hops required to migrate through the polymer electrolyte.

Existence of optical phonons in the room temperature ionic liquid 1-ethyl-3-methylimidazolium trifluoromethanesulfonate.

The technologically important properties of room temperature ionic liquids (RTILs) are fundamentally linked to the ion-ion interactions present among the constituent ions. These ion-ion interactions in one RTIL (1-ethyl-3-methylimidazolium trifluoromethanesulfonate, [C(2)mim]CF(3)SO(3)) are characterized with transmission FTIR spectroscopy and polarized attenuated total reflection (ATR) FTIR spectroscopy. A quasilattice model is determined to be the best framework for understanding the ionic interactions. A novel spectroscopic approach is proposed to characterize the degree of order that is present in the quasilattice by comparing the dipole moment derivative calculated from two independent spectroscopic measurements: (1) the TO-LO splitting of a vibrational mode using dipolar coupling theory and (2) the optical constants of the material derived from polarized ATR experiments. In principle, dipole moment derivatives calculated from dipolar coupling theory should be similar to those calculated from the optical constants if the quasilattice of the RTIL is highly structured. However, a significant disparity for the two calculations is noted for [C(2)mim]CF(3)SO(3), indicating that the quasilattice of [C(2)mim]CF(3)SO(3) is somewhat disorganized. The potential ability to spectroscopically characterize the structure of the quasilattice, which governs the long-range ion-ion interactions in a RTIL, is a major step forward in understanding the interrelationship between the molecular-level interactions among the constituent ions of an ionic liquid and the important physical properties of the RTIL.

Hydrogen-bonding and ion-ion interactions in solutions of triflic acid and 1-ethyl-3-methylimidazolium triflate.

Ion-ion and hydrogen-bonding interactions in solutions of 1-ethyl-3-methylimidazolium trifluoromethansulfonate ([C(2)mim]Tf) and triflic acid (HTf) are investigated with infrared and Raman spectroscopy. Bands indicative of highly aggregated triflate anions appear in the vibrational spectra of solutions containing a large fraction of triflic acid. These species most likely consist of triflate anions that are at least threefold coordinated by positive ions (i.e., {[C(2)mim](x)H(y)Tf}(x+y-1) where x + y > or = 3). Such coordination environments would be consistent with a larger, extended aggregate of Tf(-), [C(2)mim](+), and H(+) ions that may be charged or neutral. Evidence for hydrogen bonding between the protons and the oxygen atoms of the triflate atoms and between the hydrogen atoms of the [C(2)mim](+) and triflate anion is identified in the infrared and Raman spectra.

Salt effects on poly(N-isopropylacrylamide) phase transition thermodynamics from NMR spectroscopy.

NMR spectra were collected for cross-linked poly(N-isopropylacrylamide), poly(NIPAM), hydrogels in the presence of NaCl and CaCl2 aqueous solutions. Intensity variations in the 1H NMR signals of the polymer provide insight into the phase transition process. These data were used to observe a two-stage phase transition process. Thermodynamic quantities were obtained from a van't Hoff analysis of the temperature-dependent equilibrium constants, which were derived from the NMR data. The Delta H degrees and Delta S degrees values for the hydrogel in D2O are 3.4 kJ/mol and 11.2 J/mol.K for stage I, which is attributed to the formation of hydrophobic bonds between neighboring isopropyl groups. The formation of hydrogen bonds during stage II yielded Delta H degrees and Delta S degrees values of 14.8 kJ/mol and 48.4 J/mol.K in D2O. However, the corresponding Delta H degrees values in 150 mM NaCl and 150 mM CaCl2 are reduced to 1.5 and 1.8 kJ/mol for stage I of the dehydration process. This corresponds to the known effect of salts on hydrophobic bond energetics. The value of Delta S degrees also decreased to 4.9 and 5.9 J/mol.K in NaCl and CaCl2 solutions, respectively. However, the thermodynamic values during stage II were only slightly affected by the salts. The lower temperatures required to induce spontaneous precipitation implies that Delta G degrees of precipitation is reduced. With our measurement of equilibrium thermodynamics, we see that 150 mM NaCl and CaCl2 solutions have a greater effect on hydrophobic bond formation associated with the phase transition process. In this manner, these salts aid in solvent reorganization necessary to form the hydrophobic bond, and this suggests that the formation of hydrophobic bonds is a strong determining factor in the stability of poly(NIPAM) hydrogels in water.

Cation-anion interactions in 1-ethyl-3-methylimidazolium trifluoromethanesulfonate-based ionic liquid electrolytes.

An important step in developing ionic-liquid-based electrolytes for lithium rechargeable batteries is obtaining a molecular-level understanding of the ionic interactions that occur in these systems. In this study, 1-ethyl-3-methylimidazolium trifluoromethansulfonate ([C2mim]CF3SO3) is complexed with LiCF3SO3, and the local structures of the CF3SO3- and [C2mim]+ ions are investigated with infrared and Raman spectroscopy. The isolation and subsequent refinement of a Li[C2mim](CF3SO3)2 crystal provides further insight into the structure of the [C2mim]CF3SO3-LiCF3SO3 solutions. Minor changes are observed in the infrared and Raman spectra of dilute [C2mim]CF3SO3-LiCF3SO3 solutions compared to pure [C2mim]CF3SO3. However, a suspension of very small Li[C2mim](CF3SO3)2 crystallites forms at a solution composition of [C2mim]CF3SO3:LiCF3SO3 = 10:1 (mole ratio), placing an upper limit on the solubility of LiCF3SO3. Essentially no changes are observed in the vibrational modes of the [C2mim]+ cations over the entire range of LiCF3SO3 compositions studied, suggesting that the addition of these compounds does not significantly perturb the local structure of the [C2mim]+ cations. The salt used in this study has a common anion with the ionic liquid; thus, the ion cloud surrounding the [C2mim]+ ions, which must be primarily composed of CF3SO3- anions, is not significantly altered with the addition of LiCF3SO3.

Vibrational spectroscopic investigation of structurally-related LiFePO4, NaFePO4, and FePO4 compounds.

Vibrational spectroscopy was utilized to investigate the local structure of LiFePO(4), NaFePO(4), and FePO(4). The factor group splitting of the intramolecular PO(4)(3-) vibrations is between 10 and 20 cm(-1) less for NaFePO(4) than for LiFePO(4). This is because Li(+) ions have a higher charge density than Na(+) ions and can form stronger coordinative bonds with the PO(4)(3-) anions. Thus, the internal modes are more perturbed in LiFePO(4) and exhibit larger factor group splitting effects. The similarity of the factor group multiplets for both LiFePO(4) and NaFePO(4), particularly the PO(4)(3-) bending modes, strongly suggests that the 506 and 470 cm(-1) bands of LiFePO(4) consist almost entirely of lithium translatory motion. There are marked differences between the vibrational spectrum of FePO(4) and those of LiMPO(4) (M=Mn, Fe, Co, or Ni) or NaFePO(4). The monovalent cations interact with the oxygen atoms of the phosphate groups, affecting the frequencies and intensities of the intramolecular PO(4)(3-) modes, in a manner that is absent in FePO(4).

Modified coin cells for in situ Raman spectroelectrochemical measurements of Li(x)V2O5 for lithium rechargeable batteries.

In situ Raman spectroscopy is an extremely valuable technique for investigating fundamental reactions that occur inside lithium rechargeable batteries. However, specialized in situ Raman spectroelectrochemical cells must be constructed to perform these experiments. These cells are often quite different from the cells used in normal electrochemical investigations. More importantly, the number of cells is usually limited by construction costs; thus, routine usage of in situ Raman spectroscopy is hampered for most laboratories. This paper describes a modification to industrially available coin cells that facilitates routine in situ Raman spectroelectrochemical measurements of lithium batteries. To test this strategy, in situ Raman spectroelectrochemical measurements are performed on Li//V2O5 cells. Various phases of Li(x)V2O5 could be identified in the modified coin cells with Raman spectroscopy, and the electrochemical cycling performance between in situ and unmodified cells is nearly identical.