DOI: 10.1002/chem.
201404253 Full Paper
& Ionic Liquids
Benzene Solubility in Ionic Liquids: Working Toward an
Understanding of Liquid Clathrate Formation
Jorge F. B. Pereira,[a, b] Luis A. Flores,[a] Hui Wang,[a] and Robin D. Rogers*[a]
Abstract: The solubility of benzene in 15 imidazolium, pyrro-
lidinium, pyridinium, and piperidinium ionic liquids has been
determined; the resulting, benzene-saturated ionic liquid
solutions, also known as liquid clathrates, were examined
with 1H and 19F nuclear magnetic resonance spectroscopy to
try and understand the molecular interactions that control
liquid clathrate formation. The results suggest that benzene
interacts primarily with the cation of the ionic liquid, and
that liquid clathrate formation (and benzene solubility) is
1. Introduction
Ionic liquids (ILs), usually defined as salts with melting points
below 100 8C,[1] appeared in the last two decades as an alterna-
tive solvent for several applications,[2] such as synthesis,[3, 4]
electrochemistry,[5, 6] and liquid crystals,[7] to name a few.
Though there are a number of applications that have taken ad-
vantage of IL characteristics, such as accessible low vapor pres-
sures, high chemical, thermal, and electrochemical stabilities,
or unique solvation properties, the use of ILs in separation pro-
cesses continues to be one of the most studied applications,
because the IL’s physicochemical properties can be designed
by a proper choice of the cation and anion.[8] In this context,
the observation that several aromatic solvents, such as ben-
zene, are soluble but not completely miscible in ILs,[9] has led
to growing interest in these IL-aromatic systems.
Publications describing the solubility of aromatic hydrocar-
bons in ILs have rapidly grown,[10] but these studies have usu-
ally been aimed at the extraction of the aromatic from their
mixtures with alkanes,[11–14] or directed at thermodynamic and
modeling studies of the binary and ternary phase diagrams.[15]
Additionally, some experimental and modeling studies have
also been undertaken in order to explain the interactions that
[a] Prof. Dr. J. F. B. Pereira, L. A. Flores, Dr. H. Wang, Prof. Dr. R. D. Rogers
Center for Green Manufacturing and Department of Chemistry
The University of Alabama
Tuscaloosa, AL 35487 (USA)
E-mail: RDRogers@ua.edu
[b] Prof. Dr. J. F. B. Pereira
Current Address:
Department of Bioprocess and Biotechnology
School of Pharmaceutical Sciences
UNESP - Univ Estadual Paulista, Araraquara, SP 14801 (Brazil)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201404253.
Chem. Eur. J. 2014, 20, 15482 – 15492
controlled by the strength of the cation–anion interactions,
that is, the stronger the cation–anion interaction, the lower
the benzene solubility. Other factors that were determined
to be important in the final amount of benzene in any given
liquid clathrate phase included attractive interactions be-
tween the anion and benzene (when significant), and larger
steric or free volume demands of the ions, both of which
lead to greater benzene solubility.
control the solubility of the aromatic solvents in the ILs, after
Surette et al.[16] suggested that in some IL-aromatic systems,
liquid clathrates (LC) were formed.
Liquid clathrates were first described by Atwood et al.[17–19]
who demonstrated LC formation with highly reactive air-sensi-
tive alkylaluminum salts. Holbrey et al.[20] investigated if LC for-
mation with ILs was a general characteristic when mixing aro-
matic hydrocarbons (benzene, toluene, and xylenes) with
common 1-alkyl-3-methylimidazolium ILs ([Cnmim]X). The re-
sults demonstrated that when ILs and excess aromatic hydro-
carbons were mixed, LC phases formed spontaneously with an
upper pure aromatic phase and a lower IL/aromatic phase with
much lower viscosity than the neat ILs. This work suggested
that LC phases are formed when associative interactions be-
tween the aromatic molecules and the salt’s ions separate
cation–anion packing interactions to a sufficient degree, allow-
ing a formation of localized cage structures. Crystal structures
of IL-aromatic complexes, although not always indicative of
the solution state, have indeed shown the formation of cage
structures between benzene and 1,3-dimethylimidazolium hex-
afluorophosphate ([C1mim][PF6]), in which benzene is “sand-
wiched” between two imidazolium cations.
Although Holbrey et al. showed clear evidence that LC for-
mation in the IL-aromatic mixtures was based on cation–aro-
matic p–p interactions, some theoretical studies have demon-
strated that the p-based interactions are not the predominant
cause of the high solubility of the aromatics, rather that the IL-
cation and benzene preferential interactions are mainly ion-
quadrupole, and that the ion-quadrupole interactions between
the anion and benzene are more dominant than the cation–
benzene interactions.[21–23] As reviewed by Weber et al.,[24] there
are very complex interactions found in IL-aromatic systems, in
which the ionic nature of the IL is the main driving force for
the high solubility of aromatics, as well as for LC formation.
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This observation was supported by studies that revealed the
ability of nonaromatic ILs to solubilize aromatic hydrocar-
bons.[25, 26]
In this context, and taking into account that the molecular
interactions that control IL-aromatic LC formation are not fully
understood, we examined and report here the solubility of
benzene in various ILs as a function of varying cations and
anions, as well as 1H and 19F NMR spectroscopy studies aimed
at understanding the predominant benzene–IL interactions
behind LC formation. The studies were designed to evaluate
how LC formation is affected by cation–anion strength, prefer-
ential interactions between benzene and the cation or anion,
and steric effects. As a result of our findings, we also present
some recommendations to consider for future studies aimed
at selectivity in aromatic separations.
2. Results and Discussion
Fifteen ILs (Table 1) were chosen for this study, in order to
assess the influence of several parameters, such as hydrogen
bond acidity, basicity, aromaticity of the anion or cation, and
the length of the cationic alkyl side chains on LC formation.
The ILs investigated included the imidazolium salts, 1-ethyl-3-
methylimidazolium acetate [C2mim][OAc], 1-ethyl-3-methylimi-
dazolium dicyanamide [C2mim][N(CN)2], 1-ethyl-3-methylimida-
zolium bis(trifluoromethanesulfonyl)imide [C2mim][NTf2], 1-(2-
hydroxyethyl)-3-methylimidazolium bis(trifluoromethanesulfo-
nyl)imide [OHC2mim][NTf2], 1-butyl-3-methylimidazolium ace-
tate [C4mim][OAc], 1-butyl-3-methylimidazolium tetrafluorobo-
rate [C4mim][BF4], 1-butyl-3-methylimidazolium hexafluoro-
phosphate [C4mim][PF6], 1-butyl-3-methylimidazolium dicyana-
mide [C4mim][N(CN)2], and 1-butyl-3-methylimidazolium bis(tri-
fluoromethanesulfonyl)imide [C4mim][NTf2]; the pyrrolidium
salts, 1-butyl-1-methylpyrrolidinium dicyanamide [C4mpyrr]-
[N(CN)2], 1-butyl-1-methylpyrrolidinium bis(trifluoromethane-
sulfonyl)imide [C4mpyrr][NTf2], and 1-butyl-1-methylpyrrolidini-
um tris(pentafluoroethyl)trifluorophosphate [C4mpyrr][FAP]; the
pyridinium salts, 1-butyl-3-methylpyridinium tetrafluoroborate
[C4mpy][BF4] and 1-butyl-3-methylpyridinium bis(trifluorome-
thanesulfonyl)imide [C4mpy][NTf2]; and the piperidinium salt

Table 1. Ionic liquids studied and relevant solubility and spectroscopic data.

Ionic liquid Cation Anion Benzene xwater[a] dHHx[b] DdHHx[c] DdHHB[d]

solubility[a] neat IL [ppm] [ppm]
[mol/mol] [ppm]

[C2mim][OAc] 0.55(1) 0.062(1) 10.77 0.11 0.06

[C2mim][N(CN)2] 1.07(9) 0.063(1) 9.11 0.32 0.20

[C4mim][OAc] 1.22(1) 0.097(4) 10.84 0.14 0.09

[C4mim][BF4] 1.43(1) 0.005(1) 8.52 0.14 0.03

[C4mpy][BF4] 2.00(2) 0.023(1) 8.63 0.18 0.00

[OHC2mim][NTf2] 1.48(2) 0.002(1) 8.42 0.53 0.03

[C4mim][PF6] 2.05(6) 0.013(1) 8.25 0.37 0.03

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Table 1. (Continued)
Ionic liquid Cation Anion Benzene xwater[a] dHHx[b] DdHHx[c] DdHHB[d]
solubility[a] neat IL [ppm] [ppm]
[mol/mol] [ppm]

[C4mim][N(CN)2] 2.15(9) 0.040(4) 9.14 0.44 0.18

[C4mpyrr][N(CN)2] 2.29(4) 0.022(3) 3.65 0.53 0.24

[C2mim][NTf2] 3.25(7) 0.012(1) 8.47 0.78 0.05

[C4mpyrr][NTf2] 4.07(5) 0.044(1) 3.51 0.72 0.09

[C4mim][NTf2] 4.27(4) 0.003(1) 8.53 0.70 0.04

[C4mpy][NTf2] 4.27(9) 0.005(1) 8.61 0.70 0.02

[C4mpyrr][FAP] 4.50(21) 0.006(1) 3.17 0.88 0.00

[C4mpip][NTf2] 4.51(10) 0.004(1) 3.32 0.67 0.08

[a] The number in parenthesis is the estimated standard deviation. [b] The proton (Hx) with the highest chemical shift (dH, ppm) in the cation, usually, but
not always the most acidic proton. [c] The difference between dH, ppm of Hx in benzene solution and that in the neat IL. [d] The difference between dH,
ppm of the benzene protons in IL solution and that in neat benzene.

1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)- Figure 1 indicates that increasing the water content of

imide [C4mpip][NTf2].
Because this study included both hydrophilic ([OAc]and
[N(CN)2]) and hydrophobic ([BF4] , [PF6] , [NTf2] , and [FAP])
ILs, we first investigated how water might influence benzene
solubility. This is primarily a concern for the hydrophilic ILs,
and we thus chose one of the most hydrophilic ILs, [C2mim]-
[OAc], and prepared solutions of this IL with known water
mole fractions (xwater) from 0.05 to 0.5. The solubility of ben-
zene in these solutions was measured after the addition of 10
molar equivalents of benzene to each water/IL mixture, vigo-
rous mixing, and equilibration under ambient conditions for
12 h. Three aliquots of each lower LC phase were then taken
for 1H NMR analysis, and the mole ratio between the integrat-
ed number of protons of benzene and IL[27] was used to deter-
mine the number of moles of benzene dissolved per mole of
IL in each LC (Figure 1).
[C2mim][OAc] reduces the benzene solubility. This decrease in
benzene solubility was expected, because water solvates the IL
ions, preventing p–ion interactions with benzene. These results
do, however, emphasize the importance of using dried ILs, to
avoid water masking the “real” influence of each IL ion on ben-
zene solubility. We thus dried all of the ILs used in this study
to xwater < 0.1 (Table 1), to reduce the influence of water on the
results as much as possible.
The benzene solubility in all 15 dried ILs was then deter-
mined utilizing the same procedures as noted above. The solu-
bility and spectroscopic data obtained (Table 1) suggested dis-
tinct effects when specific cations and anions were combined,
and thus, in the discussion below, we focus on trends which
can be correlated to the anion or the cation.

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Figure 1. Solubility of benzene (mol/mol) in [C2mim][OAc] with different
mole fractions of water (xwater). The first point corresponds to the water con-
tent of the dried IL measured by Karl Fisher titration.
2.1 Anion effects
The ability of an IL to act as solvent is often reflected in the
IL’s hydrogen-bond basicity (b), mainly controlled by the IL
anion.[28] One of the methods to estimate the polarity of ILs
and, in particular, b, is the use of solvatochromic probes. Sever-
al researchers have reported polarity scales for different ILs
using different dyes and experimental approaches.[29–32 Jessop
et al.[33] compiled several solvatochromic parameters for ILs
and observed that the b values increased in the following
trend: [NTf2](0.24) < [PF6](0.29) < [BF4](0.36) <
[N(CN)2](0.52) < [OAc](0.99). Thus, in order to evaluate the
effect of different anions on LC formation, two series of imida-
zolium-based ([C2mim] + and [C4mim] + ) and one pyrrolidinium-
based ([C4mpyrr] + ) ILs were chosen with these anions and the
even more weakly basic [FAP]anion, constituting a large
range of hydrogen-bond basicity. Only those ILs commercially
available and liquid at room temperature were investigated.
The benzene solubilities from Table 1 (mol benzene/mol IL) are
compared in Figure 2.
As observed in Figure 2, the ILs with the most basic (and
most strongly coordinating) anion ([OAc]) exhibited the
lowest ability to solubilize benzene, whereas the ILs with the
least basic (and most weakly coordinating) anions ([NTf2] and
[FAP]) exhibited the highest benzene solubility. Indeed, for all
three series of ILs studied, a similar trend was observed where
the solubility of benzene decreased in the order [FAP] 
[NTf2] > [N(CN)2] > [PF6] > [BF4] > [OAc] , generally, but
not exclusively, correlated with the basicity of the anion. (The
exceptions, [N(CN)2]-based ILs, will be discussed later.) These
results would seem to indicate that, in general, the high solu-
bility of benzene is controlled by the energy of binding or co-
ordination between the anions and cations.
In order to provide a deeper understanding of these results,
we used 1H NMR spectroscopy to evaluate the chemical envi-
Chem. Eur. J. 2014, 20, 15482 – 15492 www.chemeurj.org
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Figure 2. Solubility of benzene (mol/mol) in several [C2mim] + (dark gray
bars), [C4mim] + (black bars), and [C4mpyrr] + (gray bars) ILs.
ronment of the protons in the neat IL versus the LC phase
completely saturated with benzene. The evaluation of 1H NMR
chemical shifts in ILs (particularly in the imidazolium ILs) allows
some understanding of the interionic interactions, because the
chemical shifts are proportional to the strength of such inter-
actions.[34] For each set of experiments, the 1H NMR chemical
shift deviations were defined according to Equation (1).
Dd ¼ dðIL þ benzeneÞdðILÞ ð1Þ
The results presented in Table 1 suggest a relationship be-
tween the solubility of benzene and the difference in the
chemical shift of the proton of the cation with the largest
change in chemical shift (usually the most acidic hydrogen of
the cation) in the neat IL versus the LC. In general, the addition
of benzene induces an upfield shift (negative DdH values), indi-
cating more favorable interactions of the cations with benzene
and more cation–anion separation. In previous work,[35] we
(along with other groups)[36, 37] have shown that both increas-
ing Coulombic attractions and increasing hydrogen bonding
between the cation and anion leads to downfield shifts of the
protons in imidazolium-based ILs. Notably, the exceptions were
in the [OAc]-based ILs studied, which have very limited ben-
zene solubility, for which positive DdH deviations (downfield
shift of C-2 protons) with benzene addition were observed.
To gain further understanding of the interactions controlling
LC formation, three ILs with the [C4mim] + cation were chosen
to evaluate how the benzene affects the chemical environment
of all of the imidazolium protons. For this purpose, solutions of
different benzene/IL mole ratios, 0, 0.5, 1.0, 1.5, and 2.0 mol/mol
were prepared, as noted earlier and evaluated by 1H NMR
spectroscopy. The respective DdH values for [C4mim][NTf2],
[C4mim][N(CN)2], and [C4mim][PF6] at different benzene/IL mol
ratios are depicted in Figure 3. Almost all of the protons in the
cation shift upfield with increasing concentrations of benzene.
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Figure 3. Proton chemical shift deviations (DdH) of [C4mim][NTf2],
[C4mim][N(CN)2], and [C4mim][PF6] at different benzene/IL mole ratios.
The most acidic imidazolium ring hydrogen atoms exhibit the
largest shifts, whereas the protons in the alkyl chain exhibited
much smaller deviations.
Previously, Lungwitz et al.[31, 32] showed that an IL’s b parame-
ter correlates with the 1H NMR chemical shift of the most
acidic proton of an imidazolium cation, and more recently
Cludio et al.[28] demonstrated that this proton signal could be
related to the hydrogen-bond interaction energy in the equi-
molar cation–anion mixture. Interestingly in our data, when
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comparing the different anions, it is evident that the higher
the chemical shift deviation for a given amount of benzene,
the more total benzene that IL will solubilize (i.e., DdH and
benzene solubility increase in the order [C4mim][NTf2] >
[C4mim][N(CN)2] > [C4mim][PF6]). This suggests an important
role for the anion on the cation–p interaction and consequent-
ly on LC formation, in which the anions effectively control in-
teractions between the imidazolium cation and benzene.
The data in Figure 3 also provides clues to the behavior of
the [N(CN)2]-based ILs, which, as noted earlier, were the only
exceptions to the general trend correlating benzene solubility
with the b values of the anions. These ILs (b = 0.52) exhibited
higher ability to solubilize benzene than the ILs with
[PF6](0.29) and [BF4](0.36) anions. In this particular case, it
seems that the chemical structure of the anion has some addi-
tional influence on benzene solubility in these ILs. Looking
more closely at the DdH values of [C4mim][N(CN)2] and
[C4mim][PF6] (Figure 3), it is observed that, although both sys-
tems solubilize almost the same amount of benzene (  2
mol/mol), higher deviations in proton chemical shifts were ob-
served for [C4mim][N(CN)2].
To further assess the role of ion–benzene interactions in LCs,
we also evaluated the 1H NMR chemical shift deviations of the
benzene protons (HB) in solutions of [C4mim][NTf2], [C4mim]-
[N(CN)2], and [C4mim][PF6] at different mole ratios of benzene.
The data (Table 1, Figure 4) indicates that the largest deviations
Figure 4. Benzene proton chemical shift deviations (DdH) in [C4mim][NTf2],
[C4mim][N(CN)2], and [C4mim][PF6] at different benzene mole ratios.
were obtained with [C4mim][N(CN)2], followed by [C4mim]-
[NTf2], and almost no deviations for the [C4mim][PF6] solutions.
The DdH of HB values for [N(CN)2]-based ILs of approximately
0.2 ppm were at least fourfold higher than in the other ILs.
These results suggest an interaction between benzene and
[N(CN)2]anions that was not present for the other anions stud-
ied, and this leads to an increase in the solubility of benzene.
We also note that the chemical structure of [N(CN)2] has been
previously identified to be a fairly cohesive medium due to its
capability of interacting specifically through several modes, in-
cluding lone electron pairs, dipolarity/polarizibility, and H-
bonding.[38]
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Overall, the results above indicate an important role of the
anion in IL–benzene interactions and, consequently, on the sol-
ubility of benzene. Primarily, the data suggests that anions ef-
fectively control the coordination between a solute such as
benzene and the cation; the stronger the cation–anion interac-
tion, the less benzene will be solubilized. However, Figure 2
also indicates that increasing the alkyl chain length in an imi-
dazolium cation (see [C2mim] + vs. [C4mim] + -based ILs in
Figure 2) increases the solubility of benzene. Thus, we turn to
a discussion of the results aimed at understanding how the
cation influences benzene solubility.
2.2 Cation effects
Three different [N(CN)2]-based ILs ([C2mim][N(CN)2], [C4mim]-
[N(CN)2], and [C4mpyrr][N(CN)2]) and six [NTf2]-based ILs
([OHC2mim][NTf2], [C2mim][NTf2], [C4mim][NTf2], [C4mpyrr]-
[NTf2], [C4mpy][NTf2], and [C4mpip][NTf2]) were chosen to eval-
uate the effect of the cationic core on benzene solubility and
LC formation. A comparison of the benzene solubility is pre-
sented in Figure 5 and reveals that the benzene solubility fol-
lows the trend: [OHC2mim] + < [C2mim] + < [C4mim] + 
[C4mpyrr]  [C4mpy]  [C4mpip] + .
+ +
Figure 5. Solubility of benzene in different [N(CN)2] (gray bars) and [NTf2]
(black bars) ILs.
The data suggests that both the nature of the cationic core
and the length of any appended alkyl chain can influence the
benzene solubility. Increasing the length of the alkyl chain
leads to higher benzene solubility, and the [C4mim] + -based ILs
solubilize twice the number of moles of benzene than the ILs
with the [C2mim] + cation. These results are in accord with sev-
eral studies reporting the solubilities of different aromatics in
ILs.[39–41]
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The origin of this difference is not entirely clear, however,
longer alkyl chain length can result in lower overall polarity,
while also leading to larger entropic effects. Considering the
concept of LC formation in which the benzene molecules are
entrapped by p–p stacking in the “cages” formed by two imi-
dazolium cations,[20] an increase in the “free volume” of the IL
due to steric effects would also favor increased aromatic solu-
bility.
Although we have only [OHC2mim][NTf2] as an example,
Figure 5 provides some information on the effect of functional-
ization of the cation’s alkyl substituent, in particular the influ-
ence of a hydroxyl group. The presence of the hydroxyl group
halved the benzene solubility when compared with [C2mim]-
[NTf2]. An increase in polarity by the addition of hydroxyl
groups was described previously by Chiappe et al.,[42] which, as
suggested by the authors, was caused by the significant in-
crease in the ability of the cation to act as a hydrogen-bond
donor. Increased polarity and hydrogen bonding between
cation and anion would lead to stronger cation–anion interac-
tion and, as we noted earlier, the stronger the cation–anion in-
teraction, the less benzene will be solubilized.
In contrast to the effects of the cation substituents, the influ-
ence of the nature of the cationic core appears to be much
less dramatic. For example, in the data in Figure 5, it is ob-
served that changing the cationic core in the ILs with [N(CN)2]
anions from aromatic (imidazolium) to nonaromatic (pyrrolidi-
nium) makes little difference in benzene solubility where ap-
proximately 2.2 moles of benzene per mole of IL dissolves.
Similar behavior was observed for the [NTf2]-based ILs, for
which both aromatic ILs studied, [C4mim][NTf2] and [C4mpy]-
[NTf2], have solubilities around 4.3 mol/mol and the nonaro-
matic [C4mpip][NTf2] and [C4mpyrr][NTf2] ILs have solubilities of
4.5 and 4.1 mol/mol, respectively.
As described above when analyzing the effects of the IL
anions, to evaluate changes in the chemical environments with
different cations, benzene solutions of the [NTf2]-based ILs,
which exhibited the higher solubilities, were analyzed by 1H
and 19F NMR spectroscopy. Completely miscible IL–benzene
solutions of different mole ratios up to the maximum solubility
were prepared (0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, and 4.0 mol/mol).
For each solution the 1H and 19F chemical shift deviations were
measured and the respective DdH and DdF were calculated
according to Equation (1) (for DdF the 19F NMR chemical
shift values were used). The results are presented in Figures 6
and 7.
As expected, the DdH values presented in Figure 6 were sim-
ilar in all of the [NTf2]-based ILs studied, in which all the pro-
tons shifted upfield with the addition of benzene. In all cases,
the protons at higher d (the acidic or a protons) exhibited the
highest deviations (ca. 0.5 ppm), and the protons of the
butyl-alkyl chains exhibited the lowest deviations (less than or
equal to 0.2 ppm). The 19F NMR data in Figure 7 confirm
these trends where Ddanion at different IL/benzene ratios exhibit
similar downfield shifts for all [NTf2]-based ILs studied. In all
cases, the data suggests that although the nature of each
cation is quite different, the effect of benzene on the anion–
cation interaction is almost the same.
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benzene is separating the cation

from the anion. As the anion is
separated from the cation,
cation–anion interactions are re-
duced and the polarizability of
the ions increased. Consequent-
ly, p-ion interactions with the
benzene are favored.
To understand what happened
to the protons of the benzene
when different cationic cores
were studied, all of the benzene
chemical shifts, DdHHB, were
compared at different mole
ratios of benzene/IL. The data
(see Figure 8) suggests two dif-
ferent trends. The nonaromatic-
based ILs induce two-fold higher
DdH of the HB values than the ILs
with aromatic cations, even
though the maximum benzene
solubility is essentially the same
in both types of ILs. This sug-
gests that the ILs with aromatic
cations are interacting with ben-
Figure 6. Proton chemical shift deviation (DdH) of [C4mim][NTf2] (top left), [C4mpy][NTf2] (top right), [C4mpyrr][NTf2] zene through p–p stacking, as in
(bottom left), and [C4mpip][NTf2] (bottom right) at different benzene/IL mole ratios. “free” benzene, whereas the in-

Figure 7. Fluorine chemical shift deviation of the anion (DdF) of [C4mim]- Figure 8. Benzene chemical shift deviation (DdH) in [C4mim][NTf2] (~),
[NTf2] (~), [C4mpy][NTf2] (^), [C4mpyrr][NTf2] (&), and [C4mpip][NTf2] (*) at dif- [C4mpy][NTf2] (^), [C4mpyrr][NTf2] (&), and[C4mpip][NTf2] (*) at different mole
ferent benzene/IL mole ratios. ratios of benzene/IL.

Bonhte et al.[37] suggested that chemical shift displace-

ments in imidazolium IL solutions with concentration can be
analyzed in terms of two distinct effects, namely, higher shifts
with increased hydrogen bonding and lower shifts with in-
creased p-stacking of the imidazolium cation (or any aromatic
system). The [NTf2]anions in our study are among the least
basic anions and, therefore, have weak cation–anion interac-
tion strength. Thus, as indicated above in the discussion of the
effect of anions, the lower d values determined for the cation’s
protons when benzene is added, seem to indicate that the
teractions between nonaromatic cations and benzene are of
the p-ion type.
Finally, the chemical shift trends were compared by calculat-
ing the relative deviation, R(Dd)n, of the 1H chemical shift (DdH)
of Hx (the proton of the cation with highest chemical shift) and
of the 19F chemical shift (DdF) of the [NTf2]anion (Fanion) at dif-
ferent mole ratios (n) of benzene/IL. The chemical shift devia-
tion at each benzene/IL mole ratio (DdHn or DdFn, n = 1, 2, 3, or
4) was compared to the maximum chemical shift deviations in

Chem. Eur. J. 2014, 20, 15482 – 15492 www.chemeurj.org 15488  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

saturated solutions with benzene (DdHmax or DdFmax) according
to Equations (2) and (3).
DdHn
RðDdÞn ¼
DdH max
DdFn
RðDdÞn ¼
DdF max
The values of R(Dd)n versus benzene mole ratio are present-
ed in Figure 9 and in Table S1 (in the Supporting Information).
Figure 9. Relative deviation R(Dd)n of Hx (solid symbols) and Fanion (empty
symbols) at different benzene/IL mole ratios.
The results indicate that the cation’s R(Dd)n is always higher
than that observed for the anion. It is also observed that the
highest deviation in the chemical-shift environment was ob-
served when the first mole of benzene was added, when at
least 40 % of the total deviation occurs. With the addition of
a second mole of benzene, another high deviation is observed,
roughly 30 % of the total. The first additions of benzene, there-
fore strongly affect the cation–anion interactions in which the
ions are displaced by the introduction of benzene. This “dis-
tancing” of the cation and the anion is evident until 3 moles of
benzene are added (in the case of [C2mim][NTf2] this is near
the maximum solubility of 3.2 moles of benzene). Subsequent
additions of benzene result in only small deviations in the
chemical shifts of the protons of each cation and the [NTf2]
fluorine atoms (R(Dd)n < 0.1 ppm).
Overall, this data seems to indicate that benzene solvation
of the cations, due to p–ion interactions, occurs until the IL/
benzene ratio equals 3 moles (3 benzene per cation), after
which the remaining solubility is controlled by steric or free-
volume effects, such as the longer alkyl-chain lengths of the
cation discussed above. This would essentially entrap or clath-
rate the benzene in the LC phase, but would not strongly
affect the cation–anion chemical environment. This effect clear-
ly needs further study, including effective modeling of the sys-
tems.
Chem. Eur. J. 2014, 20, 15482 – 15492 www.chemeurj.org
Full Paper
ð2Þ
ð3Þ
Figure 10. Benzene solubility as a function of the maximum chemical shift
deviations in saturated solutions with benzene (DdHmax, ppm) of the proton
with the highest d value (Hx) in the cations: (^) [OHC2mim] + ; (~) [C2mim] + ;
(&) [C4mim] + ; (N) [C4mpy] + ; (*) [C4mpyrr] + ; (+) [C4mpip] + .
3. Conclusion
A correlation was observed between benzene solubility and
the NMR chemical shift deviations for the ILs studied. Figure 10
presents a comparison between the DdH of the proton of the
cation with the highest chemical shift value (Hx) and the ben-
zene solubility for different series of ILs grouped by anion,
[OAc] , [BF4] , [N(CN)2] , [PF6] , [NTf2] , and [FAP] . The data
confirm the close relationship between the deviation in the
chemical environment of the cation’s protons and benzene sol-
ubility. In general, the benzene solubility is dependent on the
anion studied, that is, the anions that exhibit the strongest in-
teractions with the cation (e.g., [OAc] , [BF4]) have the lowest
aromatic solubilities and the anions most weakly coordinated
(e.g., [NTf2] , [FAP]) solubilize aromatics the most.
Stronger cation–anion interactions lead to lower benzene
solubility: Spectroscopic analysis supports the results dis-
cussed in Section 2.1, that the stronger the cation–anion inter-
actions, the less benzene can be solubilized. Interestingly,
almost all ILs exhibit DdH within a small range of upfield chem-
ical shifts, with the exception of the [OAc]-based ILs, in which
the cation–anion interionic interactions are much stronger,
acting more as an ion pair. Previously, Fumino et al.[43] demon-
strated that the interactions between ILs and different solvents
are dependent on two types of ion pairs, contact ion pairs
(CIPs) or solvent-separated ion pairs (SIPs). The authors sug-
gested that at infinite dilution the ions are solvated as CIPs in
weakly polar solvents, whereas for highly polar solvents they
are solvated as SIPs.
The importance of cation–anion interactions was also very
recently described for water solubility[44] and gas solubility.[45]
In the first paper, the authors observed similar trends in water
solubility as observed here for benzene, in which water solubil-
15489  2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ity increased when strongly basic anions were combined with
a cation that possesses weaker cation–anion hydrogen-bond-
ing interactions.[44] The same trends were also observed for
CO2, SO2, and H2S solubility, and Damas et al.[45] have suggest-
ed a relationship between the increase of interaction of the
gas with the anion and the weakening of cation–anion interac-
tions. Such work is helping to provide a better understanding
of the specific ions which are most likely to interact with each
solute. For example, water should strongly interact with more
basic anions (e.g., [OAc]), while benzene appears to interact
more strongly with positively charged cations. Overall, the
growing body of literature suggests that more work is needed
to understand specific interactions with each ion and how
these interactions may overcome the specific interactions be-
tween the cation and anion in an IL.
Attractive interactions between the anion and benzene lead
to higher benzene solubilities: A second aspect of the work
has shown that the anions can also have attractive interactions
with the aromatic solutes, as shown for the [N(CN)2]-based
ILs. The results indicate that ILs with [N(CN)2] anions have in-
creased aromatic solubility due to additional benzene–anion
interactions. Recently, Weber et al.[24] reviewed the intermolecu-
lar aromatic interactions with ILs, and suggested that the IL
anion could have an important role in IL–p interactions, due to
a preferential coordination of the aromatic solvents by the
polar regions of the IL. We would suggest that further study
using ILs with the [N(CN)2] anion and different aromatic com-
pounds could help understand how the anion influences the
“clathration” of aromatic solutes, as well as to determine what
molecular interactions induce such cage formation. We would
also suggest that the IL research community continue to look
for more anions with similar behavior to [N(CN)2] in order to
evaluate their potential use in increasing the selectivity for spe-
cific aromatic solutes.
Larger steric or free volume demands of the ions lead to
higher benzene solubilities: The results presented in Section
2.2 demonstrated that steric effects are also important in LC
formation. Previously, steric effects were reported by Shimo-
mura et al.[46] where NMR data suggested that in [C12mim]-
[NTf2]/benzene solution, the imidazolium ring was “sand-
wiched” between benzene molecules through cation–p inter-
actions above and below the imidazolium ring. Although, in
the system analyzed by these authors, cluster formation was
noted (as expected due to the longer alkyl chain lengths of
the cation), it is interesting to note a breakpoint in their data
correlating chemical-shift deviations at different mole ratios of
the [C12mim][NTf2]/benzene system and the respective benzene
solubility, which was probably due to the cation–anion interac-
tion. We also observed such behavior noted in Section 2.2.
4. Outlook
The study reported here has helped us to better understand
the reasons for variable benzene solubility in different kinds of
ILs and the potential for forming LCs. The next challenge will
Chem. Eur. J. 2014, 20, 15482 – 15492 www.chemeurj.org 15490
Full Paper
Figure 11. Solubility of benzene at different mole ratios (x) in [C2mim][OAc]x-
[NTf2]1x (Zero on the x axis corresponds to [C2mim][NTf2] and 1.0 to
[C2mim][OAc]).
be to use this knowledge to help understand the selectivity of
ILs for different types of aromatic compounds, such as those
used by the chemical industry in separations. We suggest the
use of multi-ionic systems (IL/benzene systems with more than
one anion and cation, which we term double salt ILs or
DSILs[47]), in which ILs with lower and higher abilities to solubi-
lize benzene are combined to clathrate the aromatics.
In our first study of this type, benzene solubility was evaluat-
ed in a DSIL we have previously characterized.[35] A strongly co-
ordinated IL, [C2mim][OAc], was combined with one of the
most weakly coordinated ILs, [C2mim][NTf2], in different mole
ratios, in order to prepare a series of systems of the type
[C2mim][OAc]x[NTf2]1x. Benzene solubility in these systems was
evaluated following the procedures outlined above and the re-
sults are presented in Figure 11.
The data in Figure 11 indicates that the benzene solubility
does not change linearly with [OAc]concentration. There is
a break point at x = 0.5 (1 mole of [OAc] per 2 moles of
[C2mim] + ). When x < 0.5, benzene solubility decreased signifi-
cantly faster with increasing [OAc] than when observed for
compositions with x > 0.5. The trends are in line with our previ-
ous studies of this DSIL[35] , which indicated preferential interac-
tions (both Coulombic interactions and hydrogen bonding) be-
tween the acetate anions compared to the [NTf2]anion with
the [C2mim] + cations. As suggested by the studies reported
here, such interactions would decrease the benzene solubility.
Overall, the data presented in Figure 11 suggest that one
could tune aromatic solubility, allowing the enhancement of
selectivity.
The use of the ILs to extract and separate aromatic com-
pounds can have significant industrial impact, and here we
aimed to provide data that would bring us closer to under-
standing what controls benzene solubility and LC formation,
thus allowing better future design of specific IL systems for
this task. Using benzene as a model solute we highlighted the
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

major interactions that we believe control the formation of LCs
including 1) the strength of the cation–anion interactions (the
main effect up to 2:1 benzene/IL mole ratio), 2) specific inter-
actions between the aromatics and anions (e.g., [N(CN)2]), and
3) steric effects or free volumes of the ions. We hope that
future molecular simulation and computational studies might
be brought to bear on the three concepts discussed above in
order to design both better ILs or IL systems and specific aro-
matic separation schemes.
5. Experimental Section
5.1. Chemicals
The ILs used in this study were: 1-ethyl-3-methylimidazolium ace-
tate, [C2mim][OAc] (95 wt %); 1-ethyl-3-methylimidazolium dicyana-
mide, [C2mim][N(CN)2] (98 wt %); 1-ethyl-3-methylimidazolium bis-
(trifluoromethanesulfonyl)imide, [C2mim][NTf2] (99 wt %); 1-(2-hy-
droxyethyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)-
imide, [OHC2mim][NTf2] (99 wt %); 1-butyl-3-methylimidazolium
acetate, [C4mim][OAc] (99 wt %); 1-butyl-3-methylimidazolium tet-
rafluoroborate, [C4mim][BF4] (99 wt %); 1-butyl-3-methylimidazoli-
um hexafluorophosphate, [C4mim][PF6] (99 wt %); 1-butyl-3-methyl-
imidazolium dicyanamide, [C4mim][N(CN)2] (98 wt %); 1-butyl-3-
methylimidazolium bis(trifluoromethanesulfonyl)imide, [C4mim]-
[NTf2] (99 wt %); 1-butyl-1-methylpyrrolidinium dicyanamide,
[C4mpyrr][N(CN)2] (98 wt %); 1-butyl-1-methylpyrrolidinium bis(tri-
fluoromethanesulfonyl)imide, [C4mpyrr][NTf2] (99 wt %); 1-butyl-1-
methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate,
[C4mpyrr][FAP] (high purity); 1-butyl-3-methylpyridinium tetrafluor-
oborate, [C4mpy][BF4] (99 wt %); 1-butyl-3-methylpyridinium bis(tri-
fluoromethanesulfonyl)imide, [C4mpy][NTf2] (99 wt %); and 1-butyl-
1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, [C4mpip]-
[NTf2] (99 wt %). All the ILs were obtained from IoLiTec (Tuscaloosa,
AL) with the exception of [C4mpyrr][FAP], which was acquired from
Merck (Darmstadt, Germany). Before use, the ILs were dried to
reduce the water content to a minimum by stirring under high
vacuum for 48 h. The water contents of the ILs were determined
with a Karl Fischer titrator (Mettler Toledo C20 coulometric KF)
using AQUASTAR CombiCoulomat fritless methanol solution, sup-
plied by Merck as titrant.
HPLC-grade benzene with a purity of  99.9 wt % was obtained
from Sigma–Aldrich (St. Louis, MO) and used as received. Deuterat-
ed chloroform (CDCl3) was purchased from Cambridge Isotope Lab-
oratories (Andover, MA). Trifluoroacetic acid used as internal sol-
vent for 19F NMR spectroscopy was acquired from Sigma–Aldrich
(St. Louis, MO) with a purity of 99 %.
5.2. Benzene solubility measurements
Experimental liquid–liquid equilibria (LLE) data were obtained by
mixing the respective ILs with 10 molar equivalents of benzene in
a vial and vortexing under ambient conditions. Spontaneous for-
mation of the LCs was observed by the increase in the IL phase
volume. After mixing, each IL–benzene system was allowed to
settle and equilibrated for 12 h for complete phase separation.
Benzene solubility and any IL in the top benzene phase were de-
termined by 1H NMR analysis. The IL concentration in the organic
phase was below the 1H NMR detection limit in all the systems
evaluated. The benzene concentration in the lower LC phase was
quantified by the molar ratio between the integrated number of
protons of benzene and of IL. Three aliquots of each LC phase
Chem. Eur. J. 2014, 20, 15482 – 15492 www.chemeurj.org
Full Paper
were examined in order to calculate the uncertainty in the deter-
mination of the solubility.
5.3. Influence of water on benzene solubility
The influence of water in ILs on the benzene solubility in the most
hydrophilic IL studied, [C2mim][OAc], was evaluated. Five different
aqueous solutions of this IL with water mole fractions (xwater) from
0.05 to 0.5 were prepared gravimetrically. Each solution was then
mixed with 10 molar equivalents of benzene, vigorously mixed,
and equilibrated under ambient conditions for 12 h. Three aliquots
of each lower LC phase were then taken to determine the benzene
solubility by 1H NMR as described above.
5.4. Spectroscopic studies of variable concentrations of ben-
zene in ILs
Several molar ratios of IL-benzene mixtures (in the completely mis-
cible region) were prepared up to the maximum benzene solubili-
ty, and 1H NMR (and 19F NMR where appropriate) analysis of each
mixture was performed. The 1H NMR spectra were obtained utiliz-
ing a 500 MHz BrukerAvance NMR spectrometer (Karlsruhe, Germa-
ny). Each sample was loaded solventless in a flame-sealed capillary,
and the spectra were collected at 25 8C using CDCl3 as the external
lock. The 19F NMR spectra were obtained on a BrukerAvance
360 MHz NMR spectrometer (Karlsruhe, Germany), using trifluoro-
acetic acid/CDCl3 solution as the external lock.
Acknowledgements
We thank the Novartis-Massachusetts Institute of Technology
(MIT) Center for Continuous Manufacturing (CCM) for financial
support.
Keywords: aromatics · benzene · cation–anion strength · ionic
liquids · clathrates
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Received: July 4, 2014
Published online on October 8, 2014
 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim