Supramolecular Structures in the Presence of Ionic Liquids
College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China 1. Introduction
Supramolecular chemistry is defined as “chemistry beyond the molecule”, bearing on the organized entities of higher complexity that result from the association of two or more chemical species held together by intermolecular forces (Lehn, 1988, 1995). Supramolecular chemistry may be divided into two broad and partially overlapping areas concerning: (1) supermolecules, well-defined and discrete oligomolecular species that result from the intermolecular association of a few components (a receptor and its substrate(s)) following a built-in scheme based on the principles of molecular recognition; (2) supramolecular assemblies, polymolecular entities that result from the spontaneous association of a large undefined number of components into a specific phase having more or less well-defined microscopic organization and macroscopic characteristics depending on its nature (such as micelles, microemulsions, vesicles, films, layers, membranes, mesomorphic phase and so on) (Lehn, 1995). Investigation on supramolecular systems is receiving more and more attention (Beletskaya et al., 2009; Constable, 2008; Descalzo et al., 2006; He et al., 2008b; Metrangolo et al., 2008; Oshovsky et al., 2007). Different from simple inorganic salts (such as NaCl) who often melt at very high temperature, ionic liquids (ILs) are a kind of organic salts that are liquid at or near room temperature, always taking 100 ºC as an upper limit. Figure 1 shows the structures of some typical cations and anions of ILs. The imidazolium, especially 1-alkyl-3-methylimidazolium (Cnmim+), is one of the most popular cations. So far, ILs have attracted much attention and been widely used as an attractive class of green solvents in the filelds of chemical reactions, organic and material syntheses, solvent extraction, and electrochemistry because of their negligible vapor pressure, nonflammability, high thermal and chemical stability, high polarity, wide electrochemical window and tunable physicochemical properties (Chiappe & Pieraccini, 2005; Dupont, 2004; Leclercq & Schmitzer, 2009a; Weingartner, 2008; Welton, 1999; Zhao et al., 2002). In the field of supramolecular chemistry, ILs could either participate directly in the assembly of supramolecular organizations, or influence the assembly of various supramolecular structures in a certain way, leading to the appearance of many novel and interesting phenomena. In addition, there exist three-dimensional supramolecular networks with polar and non-polar regions in imidazolium ILs, which can be used as powerful supramolecular receptors (Dupont, 2004; Leclercq & Schmitzer, 2009a). Therefore, this review will summarize the work in the literature, concerning the above novel and

Xinghai Shen, Qingde Chen, Jingjing Zhang and Pei Fu


Ionic Liquids: Theory, Properties, New Approaches
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Fig. 1. Structures of some typical cations and anions of ionic liquids: I: 1-alkyl-3methylimidazolium (Cnmim+); II: 1-alkyl-3-vinylimidazolium (Cnvim+); III: 1-alkylpyridinium (CnPy+); IV: tetraalkylammonium; V: tetraalkylphosphonium; VI: tetrafluoroborate (BF4−); VII: hexafluorophosphate (PF6−); VIII: bis(trifluoromethylsulfonyl)imide (Tf2N−); IX: dicyanimide ((CN)2N−); X: trifluoromethanesulfonate (TfO−); XI: nonafluorobutanesulfonate (NfO−); XII: tosylate (OTos−); XIII: alkylsulfate (CnOSO3−); XIV: tetraphenylborate (TPhB−); XV: adamantylcarboxylate (AdCO2−). interesting phenomena. The IL-relevant supramolecular systems include not only inclusion complexes with cyclodextrins (CDs), cucurbit[n]urils, calixarenes as host molecules, but also micelles, microemulsions, liquid crystals (LCs), gels. Supramolecular structures based on the host network of ILs themselves will also be presented. Furthermore, the effects of ILs on the assembly of supramolecuar systems (such as rotaxanes and polyrotaxanes, etc.) will be discussed.

2. Supermolecules systems formed by ionic liquids with different host molecules
2.1 Ionic liquids as guests for native and modified cyclodextrins 2.1.1 New structures and properties Supramolecular systems formed by ILs with CDs demonstrate new structures and properties. ILs can affect the lower critical solution temperature (LCST) of polymers consisted of CDs (Amajjahe et al., 2008; Amajjahe & Ritter, 2008a). Amajjahe et al. (Amajjahe et al., 2008) investigated the influence of three different 1-butyl-3-vinylimidazolium ILs [C4vim][Tf2N], [C4vim][NfO] and [C4vim][AdCO2] as guests on the LCST values of poly(NIPAAM-co-β-CD Methacrylate) (PNCM). The copolymer PNCM can form supramolecular polyelectrolyte-type structures, so-called pseudopolyanions through host– guest interactions with suitable ionic guests. This increased hydrophilicity of pseudopolyanions results from the free carboxylate (AdCO2−) and sulfonate (NfO−) groups, which are preferentially located in the aqueous phase and therefore responsible for the

Supramolecular Structures in the Presence of Ionic Liquids


increased LCST values. However, the complexation of Tf2N− leads to a decreased LCST value because the hydrophobic Tf2N− is preferentially located in the centre of the CD-cavity. With the increasing hydrophobicity of ILs, the cloud point of PNCM is reduced. Besides, the shrinkage and expansion behavior of pseudopolyanions could be controlled by supramolecular interaction of the CD components with three different ILs. ILs can influence the properties of CDs and vice versa. The poly([C4vim][Tf2N]) showed a pseudo-LCST effect in the presence of CD (Amajjahe & Ritter, 2008a). It was found that the CD ring complexes only the polymer anion and slips off at higher temperature when the poly(IL) becomes insoluble in water. The polymerization of ILs can be controlled by CDs (Amajjahe & Ritter, 2008b). The monomer [C4vim][Tf2N] cannot polymerize in water in the presence of β-CD by radical mechanism, which is the result of the complex formation and the spatial ion pair separation leading to quasi “naked vinylimidazolium cations” (Figure 2). This effect should be compensated with the addition of a foreign salt because of cationcation repulsion and then polymerization occurs. As a result, the controllable polymerization is realized.

Insoluble contact ion pair (in H2O)

Soluble β-CD-separated ion pair (in H2O)

Fig. 2. Host-guest complex formation of [C4vim][Tf2N] with β-CD at 298K in water. Reprinted from Amajjahe & Ritter (2008b). Besides, imidazolium salts can also be employed as carbine precursor for organometallic catalysis, where hydrogen/deuterium exchange reaction of the C(2)-proton occurs. Formation of the inclusion complexes (ICs) of imidazolium salts with the native β-CD and the heptakis-(2,6-di-O-methyl)-β-CD (DM-β-CD) is a simple and efficient method to modify the acidity of the imidazolium H(2) and its environment (Leclercq & Schmitzer, 2009b). Encapsulation of 1, 3-disubstituted imidazolium chloride by β-CDs results in the inhibition of the H(2)/D exchange in the complex. Recently, Leclercq et al. (Leclercq et al., 2009a) discovered that the imidazolium surfactants [C12mim] and [C16mim] can be used as “micellar promoters” in catalyzing hydroformylation reactions. Because of the inclusion of surfactants in the CDs, the addition of α-CD can modulate the aggregation properties of the surfactants. At high temperature, the supramolecular interactions of the imidazolium surfactants favor the micellization process. And by decreasing the temperature, CDs complex the surfactant monomers and destabilize the micelles.


Ionic Liquids: Theory, Properties, New Approaches

2.1.2 Interaction between ionic liquids and cyclodextrins The new properties of ILs on the addition of CDs originate from the interaction between ILs and CDs, mostly the inclusion complexation between them. Thus, the study on this topic is important. Various methods have been applied to investigate the interaction between ILs and CDs, such as the solubility (Gao et al., 2005a), infrared spectroscopy (Li et al., 2007c), ultra-violet spectroscopy, XRD (Gao et al., 2006c; Gao et al., 2005a; Li et al., 2007c), conductivity (Amajjahe & Ritter, 2008b; He et al., 2009), TGA (Gao et al., 2006c; Gao et al., 2005a; Li et al., 2007c), affinity CE (ACE) (Francois et al., 2007), NMR (Amajjahe & Ritter, 2008b; Gao et al., 2006c; He et al., 2009; Li et al., 2007c), fluorescence competition (He & Shen, 2008; He et al., 2009), microcalorimetry (Amajjahe et al., 2008; Amajjahe & Ritter, 2008b; Li et al.), surface tension measurements (Gao et al., 2006c) and so on. By these methods, the formation constants of ICs, the stoichiometry for ILs and CDs can be obtained. Gao et al. (Gao et al., 2005a) investigated the system of [C4mim][PF6] and β-CD using NMR and suggested that the whole imidazolium cation (C4mim+) was probably included into the cavity of β-CD, while the PF6− ion dissociated near the β-CD. They also studied ICs formation of β-CD with three kinds of IL surfactants, [C12mim][PF6], [C14mim][PF6], and [C16mim][PF6] (Gao et al., 2006c). There were two kinds of inclusion complexations, i.e., 1:1 and 1:2 (β-CD/IL) stoichiometries for β-CD-[C12mim][PF6] and β-CD-[C14mim][PF6] ICs, and only 1:1 stoichiometry for β-CD-[C16mim][PF6] ICs due to the strong steric inhibition of [C16mim][PF6]. Unlike the possible structure suggested for the [C4mim][PF6]/β-CD inclusion complex, only the alkyl side chain on the imidazolium ring of these three ILs entered into the cavity of β-CD. The similar result was obtained by Li et al. (Li et al., 2007c), which indicated that only the alkyl side chain of the [C12mim][PF6] was included into the cavity of β-CD. Francois et al. (Francois et al., 2007) developed ACE method to characterize the complex formation between seven cations of various imidazolium-based ILs ([C2mim][Tf2N], [C4mim][Tf2N], [C4mim][BF4], 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([C4dmim][BF4]), [C8mim]Br, [C10mim][BF4] and [C12mim][BF4]) and eight neutral CDs (α-CD, β-CD, γ-CD, hydroxypropyl-α-CD (HP-α-CD), hydroxypropyl-β-CD (HP-β-CD), hydroxypropyl-γ-CD (HP-γ-CD), heptakis-(2,6-di-O-methyl)-β-CD (DM-β-CD) and heptakis-(2,3,6-tri-O-methyl)-β-CD (TM-β-CD)). According to classical nonlinear and linear treatments, they obtained the complex stoichiometry and formation constant K. The majority of systems followed a 1:1 complexation stoichiometry model but in four cases ([C10mim][BF4], [C12mim][BF4] and α-CD, DM-β-CD) a 1:2 stoichiometry was better satisfied. It was established that the main factor influencing the strength of the inclusion complexation was the length of alkyl side chain on the imidazolium ring. The presence of a methyl group at the C(2) position and the nature of anion associated to the imidazolium cation in the IL did not show significant influence on the complexation constant obtained. Also, the size of the CD cavity noticeably impacts the stability of the 1:1 complexes, with stronger complexes being given by β-CD. Furthermore, it was shown that two CD molecules can likely be threaded along C10 and C12 alkyl side chains and there was no inclusion of the imidazolium ring into the cavity of β-CD. Mostly, the interaction of CDs and ILs are studied in aqueous solution. Recently, it was investigated that the dissolution of β-CD could be enhanced in some hydrophilic ILs and 1:1 inclusion complexes were formed between β-CD and imidazolium cations of the ILs (Zheng et al.). Differently, several inclusion complexes of β-CD with anion of ILs were also reported. As mentioned in Section 2.1.1, the anion Tf2N− of [C4vim][Tf2N] formed exclusively host-guest

Supramolecular Structures in the Presence of Ionic Liquids


complex with β-CD (Amajjahe et al., 2008; Amajjahe & Ritter, 2008b). Similarly, the anion PF6− but not the cation C4vim+ was found to be accommodated by β-CD. We reported that [C4mim][PF6], [C4mim][BF4], and [C4mim]Cl formed 1:1 inclusion complexes with β-CD, respectively (He & Shen, 2008). Through 19F NMR, we also found that PF6− and BF4− could interact with β-CD but the latter interaction was relatively weak.

Fig. 3. Two-Step Equilibrium in an IL/β-CD System (Path I: the cation interacts with β-CD more strongly than the anion does, Path II: the anion interacts with β-CD more strongly than the cation does). Reprinted from He et al. (2009). Considering the above studies, a general pattern in the IL/β-CD system and a two-step equilibrium was brought forward as shown in Figure 3. It was confirmed that the alkyl side chain on the imidazolium ring but not the imidazolium ring itself entered into the cavity of β-CD. As for the IL [C12mim][Tf2N], the cation and the anion both exhibited strong interactions with β-CD simultaneously (He et al., 2009). It was suggested that the strength of the interaction of various cations and anions in ILs with β-CD follows the following order: NfO− > C12mim+ > Tf2N− ~ AdCO2− ~ C10mim+ > C8mim+ > 1-hexyl-2,3-dimethylimidazolium cation (C6dmim+) ~ PF6− > BF4− > 1-butyl-2,3-dimethylimidazolium cation (C4dmim+) ~ C4vim+ ~ C4mim+ > Cl−. Leclercq et al. (Leclercq & Schmitzer, 2008) discovered multiple equilibria in the complexation of dibenzylimidazolium bromide by CDs. In aqueous solution, dibenzylimidazolium bromide forms dimeric assemblies by T-stacking between an acidic proton of the imidazolium and the benzyl aromatic ring of another cation (Figure 4). This dimeric association can be disturbed by the addition of native CDs. The control of the majority species in solution can be made by the judicious choice of CD concentration and its

Fig. 4. Structure of the dibenzylimidazolium bromide water dimer obtained by PM3 in accordance with the crystalline structure and the conventional representation adopted in this study. Reprinted from Leclercq & Schmitzer (2008).

4-phenylene)bisimidazolium dibromide salts and CB7 were studied. from C1mim+ to C6mim+. to take advantage of the ion-dipole interactions. 2009). At the same time. the preferred binding location(s) on CB are the carbonyl-lined portals. the binding constant between ILs and CB7 increases (Miskolczy et al. Reprinted from Leclercq & Schmitzer (2008). macrocycle size. the dimer is dissociated to form a 1:1 IC. With cationic organic or organometallic guests. nBu).1′-dialky-3. with the smaller guests inside its cavity. rather than at the carbonyl-lined portals by the study of NMR. C1mim+ forms a fairly stable complex with Cucurbit[7]uril (CB7). as these charge-diffuse peralkylated onium cations. With simple hydrophilic cations. The complex formation of ILs and CBns is not all the same with CDs because of the different structure between them (Montes-Navajas et al. With cationic guests. the fact that the anion barely influences the binding constant of IL-CB7 complexes is probably due to the significant negative charge density of the carbonyl-laced portals of CB7. they discovered that the stability constants are dependent on the size and coordination number of the central atom and . St-Jacques et al. However. The dimer is complexed directly by β-CD. Equilibrium distributions for the formation of I2· CD2 from I2 in the presence of (a) αCD and (b) β-CD. Moreover. because a growing segment of the carbon chain cannot be confined in CB7. such as protons. 2. CB7 has a less polar cavity than β-CD. Et.. NR4+. very strong binding is achieved when the cationic portion(s) of the guest can be positioned near the portals. 5. 2008). respectively. 2008) studied the position of charge-diffuse peralkylated onium cations. as the numbers of carbon atoms in the aliphatic chain grows. the stoichiometry of the complexes not only depends on the alkyl chains. which could be the cations of ILs. in the cavity of CB7. which disfavors the ion pairing. but also lies on the relative concentration of the imidazolium salt and CB7 (Noujeim et al.. Different cations prefer to locate in different positions of CB. alkali metal and alkali earth cations and transition metal ions. (St-Jacques et al. further lengthening of the alkyl group destabilizes the complex. PR4+ and SR3+ (R=Me..2 Ionic liquids as guests for Cucurbit[n]uril system Cucurbit[n]uril (CBn) is another important host molecule in supramolecular chemsitry. Unlike β-CD. the stability constants of the CB are larger that those of the corresponding CDs and can be several orders of magnitude larger when the guest is a dication. at higher concentration. which hinders the interaction with anions. When inclusion complexes between 1. when considering size selectivity.. New Approaches Fig. 2009). nPr. similarly. I and I2 represent the dibenzylimidazolium bromide salt and the dimer.3′-(1. this 1:1 complex can dimerize (Figure 5).432 Ionic Liquids: Theory. Properties. whereas in the presence of α-CD. However.

6. 1-alkyl-3-methylimidazolium type ILs can modify the fluorescent properties of the complex much more efficiently than NaCl. Two different modes of inclusion binding between 1-alkyl-3-methylimidazolium guests and CB6. for example berberine. According to 1H NMR titration experiments. C2mim+ and C4mim+ demonstrated different binding modes with CB6. 2:1 stoichiometry between C2mim+ and CB6 provides opportunities for a new type of selfassembly with CB6. such as pH and the other compounds. inclusion complex formation can be used to separation processes. which can facilitate the detection of berberine even below nanomolar concentration. On the other hand. Interestingly. It is the result that the formation of ternary complex by time-resolved fluorescence studies. because berberine fluorescence is insensitive to the environment..Supramolecular Structures in the Presence of Ionic Liquids 433 the size and hydrophobicity of the alkyl group. The results can be applied in enzyme assays. Commonly. CB6 was pulled into neutral water through encapsulation of an imidazolium-based IL (Liu et al. 2008). However. Because [Cnmim]Br is only capable of . 2009).. When using CB7 as macrocyclic host compound. All imidazolium guests form 1:1 complexes with CB6. Fig. inclusion complex formation with CB7 can be applied to enhance the fluorescence response of guest (Megyesi et al. a very stable 1:1 inclusion complex formed and led to about 500-fold fluorescence intensity enhancement. 2008). The interaction of CB6 and [Cnmim]Br was found to significantly increase the solubility of CB6 in neutral water (Zhao et al.. the formation of 1:1 complex between C2mim+ and CB6 was found recently (Kolman et al. Reprinted from Kolman et al.. The small changes in alkyl chain length can dramatically increase the solubility of CB6. (2009). Besides. The imidazolium aromatic ring is polarized upon complexation with CB6 and the electron density shifts from the nitrogen located in the proximity of the carbonyl portal of CB6 toward the opposite nitrogen atom. the mode of inclusion binding depends on the length of the alkyl substituent (Figure 6). The CB7 has a preference for Et over Me for NR4+ and SR3+ and the opposite for PR4+. a clinically important natural alkaloid. The supramolecular interaction between series of 1alkyl-3-methylimidazolium guests with variable alkyl substituent lengths and CB6 in the solution and the solid state was studied. Cucurbit[6]uril (CB6) is poorly soluble in water and insoluble in organic solvents. The change of association constant and the fluorescence quantum yield of the complex can be accomplished by the addition of NaCl. with trends of PMe4+ > NMe4+ > SMe3+ and SEt3+ > NEt4+ > PEt4+ in binding constants with CB7. However. 2010).

liquid crystals and vesicle) in ILs. in which IL participated in the formation of micelles. but enhanced the stability of Calix-S6 complexes. Moreover. 2009. The stability of Cnmim+-Calix-S4 complex was significantly larger than that of Cnmim+-Calix-S6 supramolecules due to better size match in the former case. which acted as the solvent (Hao & Zemb. It was investigated that the imidazolium head group resided in the calixarene cavity and the terminus of alkyl chain penetrated the adjacent hydrophobic bi-layer. . The lengthening of the aliphatic side chain of the imidazolium moiety diminished the equilibrium constant of the complexation with Calix-S4. 2007) studied the inclusion complexation of psulfonatocalix[6]arene (Calix-S6) with three kinds of phenothiazine dyes in a mixture of [C4mim][BF4] and ethanol. Besides. the strength of Cnmim+ inclusion in Calix-S6 was anion independent. 3. 2010a. In this part. in which ILs replaced oil. imidazolium or bis-imidazolium cations.3 Ionic liquids as guests for Calixarene system Inazumi et al. the inclusion complex formation of Cnmim+ type ILs with Calix-S6 and p-sulfonatocalix[4]arene (Calix-S4) was verified by the fluorescence competition method with berberine alkaloid as fluorescent probe (Miskolczy & Biczok. lyotropic liquid crystal and vesicle.1 IL based micelles (ionic liquid as surfactant) Micelles generally form in water and the hydrophobic effect is the main driving force. 3. 2009). 2007). Hao et al. reviewed the self-assembled structures (such as micelles. CB7-[Cnmim][Br] can be removed from the mixture and realize the isolation of CB7 (Jiao et al. 2010). water or surfactants. 2008).. 2.. Supramolecular assemblies based on ionic liquids Generally. Qiu et al. such an interaction is not feasible because the negative charge of the macrocycle prevents anion ingression into the cavity of the host. Properties. microemulsion. Very recently. It was different from the characteristics of ILs in β-CD because of ion pair formation within the β-CD cavity. we summarized the IL based organized assemblies. micelles formed in nonaqueous polar solvents (including ILs) have been reported. In the case of Cnmim+-Calix-S6 complex. comprising of the calixarenens and phosphonium ions. long-chain ILs can act as ionic surfactants and form similar self-assembly in water or oil. The influence of the length of the aliphatic side chain was opposite for Calix-S4 and Calix-S6.434 Ionic Liquids: Theory.. microemulsions. summarized the studies of IL based microemulsions from the perspective of the role of ILs (Qiu & Texter. The larger conformational mobility of Calix-S6 compared to that of Calix-S4 rendered the larger macrocycle more adaptable to the geometrical features of Cnmim+ permitting stronger host-guest interaction when the aliphatic chain of Cnmim+ is longer. Ling et al. reported the multicomponent materials containing Calix-S4. It was found that a competing complexation happened between the included dye and the IL molecules and that the 1:1 inclusion complex was formed by C4mim+ and Calix-S6. it is also a green process since imidazolium ILs can be reused. b). They demonstrated that the electrostatic attraction between Cnmim+ ion and the sulfonato groups at the upper rim of calixarene macrocycle was not the dominant driving force of complexation. vesicles and liquid crystals rather than acted as solvents. As for the anions. amphiphilic molecules self-assemble to form micelle. (Inazumi et al. New Approaches binding with CB7 in a CB5/CB7 mixture. ILs participated in the formation of the microemulsions. phosphonium cations and different lanthanide ions (Ling et al. microemulsions. Recently.

2008a.. Blesic et al. Whereas. Vanyur et al. 2007.. 2008b.. 2008b. Modaressi et al. Dong et al. In addition. 2007.031 M). 2009. Results showed that the long chain imidazolium ILs acted as ionic surfactants and stronger aggregation tendency of the ILs might be attributed to characteristic nature of imidazolium head group such as potency of H-bond formation. It was proposed that the short-chain [C4mim][BF4] formed polydisperse spherical aggregates. The aggregation number of the ILs was found to increase with the increasing length of the alkyl chain and a possible microscopic aggregation structure such as stairs has been proposed (Zhao et al. 1-methyl-3-octylimidazolium chloride produced inhomogeneous solution of larger aggregates. ILs based on the 1-alkyl-3-methylimidazolium cation (Cnmim+) possess an inherent amphiphilicity.. electrical conductivity measurements and fluorescence techniques et al. Luczak et al. (Blesic et al. which were dissolved on the addition of more than 2:1 molar excess of sodium dodecylsulfate (SDS) due to the formation of mixed micelle. 2008a).. whereas the [C8mim]I formed regularly sized micelles above the cmc... Aggregationinduced conformational changes in different ILs were shown to depend on the aromatic ring. The aggregation behavior of 1-alkyl-3-methylimidazolium ILs in aqueous solutions has been investigated (Bowers et al. the aggregation of amphiphilic copolymers and surfactant-like ILs in ILs was reported. 2008. which may result in the larger size of the aggregates in ILs than that in aqueous systems (Figure 7) (Li et al.. Zhao et al.. 2007.Supramolecular Structures in the Presence of Ionic Liquids 435 Because of the existence of electrostatic repulsion among the hydrophilic groups. 2007. Wang et al. Miskolczy and his coworkers (Miskolczy et al. 7.. Wang et al. Dong et al. 2008. Luczak et al.. Zhang et al. such as surface tension. which is lacking in common ionic surfactants. 2007.. 2008a).... 2007. respectively. Fig. Dong et al. Reprinted from Li et al.. (2008a). In recent years. Jungnickel et al. 2008. 2007. Schematic representation of long-chain IL aggregates in water (a) and in [C4mim][BF4] (b). counterions. 2004). 2008.. 2008. 2004) investigated the association of ILs possessing n-octyl moiety either in the cation or in the anion in aqueous solution. Fluorescence quenching . alkyl chain. El Seoud et al. Hollow ellipses and hollow circles represent the cations and anions in ILs. 2008a). The micelle formation of surface active [C2nmim]+ (n = 4~8) in aqueous solution was investigated by several methods.. Inoue et al.. surfactant behaviors of such ILs received much attention. and their interactions with water. 2007b.. surfactant molecules are kept apart and loosely arranged. Singh & Kumar. It was found that 1-butyl-3-methylimidazolium octyl sulfate acted as a surfactant above cmc (0.

For both ILs. s= 2. 1-propanol. Whereas for shorter-substituent cations. 8. increases in the cmc values and minimum surface area per surfactant molecule. 2008). no aggregates formed due to the less hydrophobic interaction than the electrostatic repulsive interaction between the cations and the counter anions (Zhao et al. Properties. 1-butanol. [C16mim]Br was used as a new cationic surfactant for separation of phenolic compounds by MEKC (Niu et al. They also mentioned that ILs can be used to improve the solubility of hydrophobic compounds. (Dorbritz et al. and acetonitrile) by surface tensiometry. 2008a) studied the aggregation of surface active [C16mim]Br and reported the formation of wormlike micelles in the presence of salts. adsorption efficiency and effectiveness of surface tension reduction were obtained when increasing the organic solvent content.. . and the steric repulsion between the head groups of the cations. 2009). decreases in the maximum surface excess concentration.. Reprinted from Blesic et al. Fig. 2009). ILs based on imidazolium and ammonium salts with longer-substituent cations selfassemble on negatively charged polyimide substrates via electrostatic force.... similar to the situation of some traditional ionic surfactants in aqueous solution.436 Ionic Liquids: Theory. Zheng and his coworkers (Dong et al. 2005) found that the formation of aggregates of [C4mim][BF4] and [C4mim][Tf2N] in aqueous solution depended on the solvent. The ring type of the cations also had significant effect on the aggregation behavior of the ILs. 2009) studied the micellar properties of aqueous solutions of two ILs. 4. which was controlled mainly by the balance among the factors of hydrophobicity of the cations. binding strength of the cations with a given anion. Dorbritz et al. the IL concentration and the anion structure of the ILs. 2008). and the micellization was entropy-driven when s=2 and 4. The former two factors promote but the latter factor weakens the aggregates formation. 2008b). Results showed that the surface activity of [C12–s–C12im]Br2 decreased with increasing spacer length. Anderson’s group (Pino et al. Also. General structure of 1-alkyl-3-methylimidazolium alkylsulfonate ILs ([CnH2n+1mim][CmH2m+1SO3]). and explained by the hydrated radius or Gibbs energy of hydration of the anions (Wang et al.. whereas aggregation of [C12–6–C12im]Br2 is enthalpy-driven at lower temperature but entropy-driven at higher temperature (Ao et al. m+n is the sum of the number of carbon atoms in the two alkyl-substituents. 1-hexadecyl-3-butylimidazolium bromide and 1. 6) have been investigated... 1-pentanol. The influence of the anions on the aggregation of ILs was first reported by Wang et al.. New Approaches method in which pyridinium ILs acted as quenchers was firstly used to detect the aggregation behavior of surfactant ILs (Blesic et al. The aggregation behavior and thermodynamic properties of micellization for the IL-type Gemini imidazolium surfactants with different spacer length ([C12–s–C12im]Br2. (2009b).3-didodecylimidazolium bromide. in the presence of several organic solvents (methanol.

[CnH2n+1mim][CmH2m+1SO3] (Figure 8). When the amphiphilic character is present in both the cation and anion (n = 4 and 8. showing a decrease of the cmc with the increase of the alkyl chain length in the cation. in another IL ethylammonium nitrate (EAN). Recently. where the structures due to electrostatic interactions can persist at such high temperatures. 2007) have reported the aggregation behavior of surfactant-like ILs.. have been investigated for the first time by Blesic et al. 2006a). General structures of the new fluorous ILs. m = 4 and 8). The aggregation behavior of a series of long-chain ILs. Gao et al. Li et al.2 Ionic liquid based microemulsions IL based microemulsions... and direct observation. 9. and 12) behaved as conventional cationic surfactants. 2006d.Supramolecular Structures in the Presence of Ionic Liquids 437 Anionic and cationic alkyl-chain effects on the self-aggregation of both neat and aqueous solutions of 1-alkyl-3-methylimidazolium alkylsulfonate salts. 10. which utilize ILs to replace one or more components of classical microemulsions. (Blesic et al. 2007b.. 2007b). (2000). a synergistic packing effect appears to lead to the formation of novel catanionic surfactants with both cmc values lower than anticipated. 2009) applied molecular dynamics (MD) to study the cation aggregation of [C10mim]Br in aqueous solution and found that the chains were buried inside the micelle to avoid unfavorable interactions with water. First of all. Fig. in [C4mim][BF4] was studied by Li et al. They compared the effects of the alkyl-substitution patterns in both the cation and anion on the surfactant properties of these salts.. are so attractive that lots of papers have been published to characterize these kinds of IL based microemulsions. (Li et al. [C2nmim]Br (n = 5∼8). leaving the polar headgroups exposed to water. 2004. Gao et al. have been extensively characterized by a number of techniques. Davis and his coworkers (Merrigan et al. IL based microemulsions. Gao et al.. 2000) synthesized four new surfactant fluorinated ILs (Figure 9) and reported the formation and stabilization of dispersions of perfluorocarbons in [C6mim][PF6] for the first time. [C16mim]Cl and [C16mim][BF4]. where the phase boundaries were determined by observing the transition from transparency to . Kunz et al.. The results indicated that the cmc for the long-chain ILs in [C4mim][BF4] are much larger than that in water and diameters of the spherical aggregates obtained by freeze-fracturing electron microscopy (FFEM) and dynamic light scattering (DLS) measurements were 70∼100 nm. (Thomaier & Kunz.. Bhargava and his coworkers (Bhargava & Klein. It was found that the ILs with methylsulfonate anions (n = 8. 2008a) for the first time. in which ILs replaced water of traditional microemulsions. Microregion of phase diagram of IL based microemulsions was detected by cyclic voltammetric technique (Gao et al. 3. Reprinted from Merrigan et al. 2006b. 2009b).. and enhanced surface activity. electrical conductivity (Gao et al.

Li et al.. Sarkar and his coworkers (Adhikari et al.. 2008b). It was proposed that the electropositive imidazolium ring of IL destroyed the hydrogen-bonding between TX-100 molecules. Hence.. Gao et al. 2006b).. 2009c) reported the phase diagram of p-xylene-[C14mim]Br-water ternary system... 2007b) studied the reversed microemulsion of TX-100 in toluene with [C4mim][BF4] cores. New Approaches turbidity (Cheng et al. Li et al. 2007b) initiated the work of applying steady-state and time-resolved fluorescence spectroscopy to investigate IL based microemulsions. For the [C4mim][BF4]/TX-100/benzene microemulsion. 2006b. 2004. small-angle X-ray scattering (SAXS) (Li et al. 2006b. Li et al. 2005b.. Cheng et al. [C4mim][BF4]/TX-100/p-xylene reversed microemulsion was investigated and a plausible structure with “IL pool” was presented (Gao et al. Li et al. (Cheng et al.. Cheng et al.. Gao et al. Gao et al. 2006b... 2007a. 2007b) reported the first microemulsion formed by two ILs.. 2005b. water located in the palisade layers and made a base environment which might be used to prepare metal hydroxides and metal oxides (Li et al. Seth et al.. Successive addition of [C4mim][BF4] led to the appearance of large-sized microemulsion droplet clusters (Gao et al. Gao et al. Additionally. 2006b).. Gao et al. 2007b. The formation of IL based microemulsion in supercritical carbon dioxide with N-ethyl perfluorooctylsulfonamide was reported (Liu et al.. Gao et al. 2005) have been applied to characterize the microemulsions with polar IL cores. FFEM (Cheng et al. i.. 2008b. 2007b). Gao et al. DLS (Cheng et al. 2008b. These techniques proved the swollen of reversed micelle with the addition of IL. Gao et al. and then became constant. (Li et al. ILs may also replace the other components of traditional microemulsions.. In the [C4mim][BF4]/TX-100/thriethylamine microemulsion. With the addition of [C4mim][BF4] into TX100/toluene micelle.. In this field.. Coumarin 151. The results showed the solvation time inside the polar cores of the microemulsions was retarded compared to that in neat IL because of restrictions in the ionic motions imposed by the microemulsions. water molecules interacted with oxyethylene (OE) units of TX-100 through hydrogen-bonding and attracted electropositive imidazolium ring of IL with electronegative oxygen (Gao et al.. 2009). 2009a) considered the hydrophobic interaction between the added organic solvents and hydrophobic groups of surfactant molecules to be the driving force in the formation of oil-in-IL (O/IL) microemulsions (Figure 10). Zheng and his coworkers (Li et al.. lamellar lyotropic liquid crystals or microemulsions formed depending on the composition. The effect of additional water on the microstructure and properties of IL based microemulsions has been studied.. Cheng et al. 2007b). 2008b. Gao et al. They observed a bicontinuous microstructure by FFEM for the first time with successive addition of organic solvents.. indicating the formation of “IL pool”. UV-vis spectroscopy (Gao et al.. 2007).. where hexagonal... Li et al. 153 and 490 were adopted as the probes.. 2008b).. Gao et al. The first microemulsion comprising an IL ([C16mim]Cl) as surfactant and another IL (EAN and [C4mim][BF4].. Gao et al.. 2008b). Properties... 2007a. 2006b. 2006.. 2005..e..438 Ionic Liquids: Theory. 2005a). which indicated the formation of reversed microemulsion. (Gao et al. 2007b) and conductivity measurements (Gao et al. Chakrabarty et al. More detailed information was gained through FTIR (Gao et al. 2007a).. respectively) as polar pseudo-phase was presented (Zech et al.. 2007a.. 2007. Seth et al. Gao et al. Based on the phase diagram. hydrophobic [C4mim][PF6] and hydrophilic propylammonium formate (PAF). 2004. 2008. 1H NMR (Gao et al. They confirmed the formation of oil-in-water (O/W) microemulsion through the linear increasing volume of the droplets with added p-xylene. Gao et al.. using methyl orange and methylene blue as probes. 2005b. 2007a. 2005a). the amount of solubilized [C4mim][BF4] enhanced with the increase of water content ... 2005a) and smallangle neutron scattering (SANS) (Eastoe et al. the polarity of the microemulsion increased firstly. 2007a.

which was further confirmed by conductivity measurements. whose properties are intermediate between that of the crystalline solid state and that of the liquid state. the magnetic susceptibility.3 Ionic liquid based lyotropic liquid crystal systems Liquid crystals are liquid anisotropic compounds. and water at 298 K. Davis and his coworkers (Davis et al. which exhibited lyotropic liquid crystalline behavior while inducing the gelation of benzene. 2008a). The investigations of the lyotropic liquid crystalline phase formation containing ILs are also of great interest. However. 3. and the mechanical properties of a liquid crystal depend on the direction in which these quantities are measured (Binnemans. Chen and his coworkers (Zhang et al... Firestone’s group reported that lyotropic liquid crystalline formed in [C10mim]Brwater (5-40% wt%) system (Firestone et al. because the water molecules were like “glue” that stuck the IL and OE units more tightly together. The refractive index. the electric permittivity. 2007) reported the formation of two lyotropic liquid crystals formed in a ternary system of [C16mim]Cl. 2005). (2009a).. The opposite effects caused by the water added on IL based microemulsions with same composition except continuous oil attracted us to study the role of the water. 2002). where one was the hexagonal phase connected to the [C16mim]Cl-water axis and the other was the lamellar phase in the center in the phase diagram (Figure 11). 1998) obtained a novel IL by anion metathesis with NaPF6 after the imidazole-ring miconazole reacting with alkyl iodides to form imidazolium cations. The formation of liquid .Supramolecular Structures in the Presence of Ionic Liquids 439 Fig. an increase in the amount of water in [C4mim][BF4]/TX100/cyclohexane microemulsions led to the phase separation and a remarkable decrease in the size of droplets (Gao et al... Reprinted from Gao et al. They also obtained anisotropic gold nanoparticles with a variety of sizes and morphologies in the nanostructured [C10mim]Clwater ionogel template by photochemical reduction of HAuCl4 (Firestone et al. the number of droplets increased. Therefore. 1-decanol. 2005). 10. Schematic diagrams of solution environments before (left) and after (right) adding organic solvents to the mixture of TX-100 and [C4mim][BF4].

i. and water. high stability and viscosity.440 Ionic Liquids: Theory. formed in the ternary mixtures of [C16mim]Br/pxylene/water. Sectional schematic graph of possible structures formed in the hexagonal and lamellar phases. whereas [C4mim][BF4] was mainly located in the water layer of hexagonal phases and therefore. crystalline phases is believed to arise from a hydrogen-bonded network comprised of an imidazolium ring. 2007). Wang et al.. 1-decanol. anion.. 2009b). H-bonded network comprising H2O. Two types of lyotropic liquid crystalline phases. In addition. 2007) .. hexagonal and lamellar. 11. Cl−. 2009b).. However. 2009). with p-xylene and water were studied by Li et al.. (Ge et al. (Friberg et al. the strength of the network of hexagonal phase formed in the Brij-97/water/[C4mim][BF4] system was stronger than that of the Brij-97/water/[C4mim][PF6] system. The hexagonal lyotropic liquid crystalline phase formed in the ternary system of the [C12mim]Br in aqueous solution of [C4mim][BF4] (Wu et al. 2000) studied the solubilization of [C4mim][PF6] in the lamellar phase of Brij-30/water system. where the lattice parameters depended on the content of surfactant and water (Zhang et al. It was reported that a lamellar phase could be formed in aqueous solutions of Brij-97 by solubilizing [C4mim][PF6] and [C4mim][BF4] (Wang & Zhou. (2007). As a kind of co-surfactant. ILs are superior to alcohol because of its negligible vapor pressure.. and C10H21OH (top). Reprinted from Zhang et al. Properties. Ge et al. 2005) determined the phase diagram of ternary system of Brij-97/IL ([C4mim][PF6] or [C4mim][BF4])/water and investigated the location of IL in the hexagonal liquid crystal. Friberg et al. Phase behaviors of three long-chained imidazolium ILs. the imidazolium cation.. New Approaches Fig. For the first time. [C12mim]Br. [C4mim][PF6] was dominantly penetrated between the OE chains of surfactant molecules. (Wang et al.e. it was found that the cylindrical units compacted much denser for the hexagonal phases formed by [C12mim]Br in comparison with that formed by dodecyltrimethylammonium bromide (DTAB). the formation of a lyotropic bicontinuous cubic phase in imidazolium-type IL system was reported (Li et al. [C14mim]Br and [C16mim]Br. and the results showed that IL can be solubilized into the lamellar phase without changing the dimensions of the amphiphilic layer. the reports on the molecular aggregations using IL as co-surfactants are still scarce in the literature.

Reprinted from Ge et al. Ma et al. Diakyldimethylammonium bromide formed bilayer membranes in the designed IL systems and ionophilic ether groups of ILs were found to be indispensable for the stable solvation of ammonium bilayers (Nakashima & Kimizuka.. 12. 2002). Generation of vesicles from single surfactants or from mixtures of anionic and cationic surfactants has been reported over the last several years. The weight ratio of B is Brij-30: [C4mim][PF6]: H2O = 54:6:40. 2008) found that the addition of very small amounts of an alcohol or water into tri-ndecylmethylphosphonium chloride and bromide salts (1P10X) induced the formation of liquid crystalline. found that the addition of [C4mim][BF4] could promote the crystallization of lysozyme. where the structure strength was enhanced by increasing the amount of Brij-30 and [C4mim][PF6] and impaired with the increase of water content. Su et al. Structure illustration (A) and typical micrograph (B) of lamellar phase in Brij30/[C4mim][PF6]/H2O system. (Xiao et al. where strong association between the hydroxyl groups of alcohol or water and the head groups of 1P10X is indicated. 3. [C4mim][PF6] and water (Figure 12). reported the microstructure of lamellar liquid crystal composed of Brij-30.4 Ionic liquid based Vesicles and gels Vesicles represent one class of self-assembly formed by phospholipids and synthetic surfactants. where the thermal and phase behaviors can be modulated by changing the spacer length (methylene units in azo). little attention has been given to the protein crystallization system where IL is added.. 2008) fabricated a new type of thermotropic liquid-crystalline photosensitive supramolecular ionic self-assembly of polyelectrolyte and functional unit azobenzene IL crystal (azo-ILC). (Ma et al. Li et al. This is the first report which supported . 2008c). The lubrication properties of the ternary system were investigated and the effect of IL on the lubrication properties of traditional lamellar phase was confirmed.Supramolecular Structures in the Presence of Ionic Liquids 441 Fig. However.. which was probably resulted from the influence of the ionic polarization and kinetics in the lysozyme crystallization (Li et al. (2007).

Strong electrostatic interactions between bulky organic ions are the main force of the formation of vesicle aggregates. Both the hydrophobic interaction of alkyl chains and interactions between oppositely charged head groups played important roles for the gel formation. ILs are considered as homogeneous solvents. we illustrate the self- . Reprinted from Tan et al. The similar ion conductivities of [C4mim][PF6] gels to those of the pure [C4mim][PF6] indicated that the supramolecular structures in the [C4mim][PF6] gels had apparently no effect on the mobility of the ions. 2006) reported that Brij-76 were temperature dependant on the selfassembly processes in [C4mim][BF4]. The self-assembled surfactant vesicles formed by the fluorous surfactant Zn(OOCCH2C6F13)2 or by mixtures of tetradecyldimethylamine oxide (C14DMAO) and Zn(OOCCH2C6F13)2 were reported by Hao’s group (Hao et al. Kimizuka and his coworkers (Kimizuka & Nakashima. 2001) reported that stable bilayer membranes formed when glycolipids were dispersed in sugar-philic ether-containing ILs.. 13. which have already been extensively reviewed in the literature (Dupont. similar to the normal molecular solvents. 90 and 110 ºC. Tan et al. It was found that a novel gel phase with quite high water content could be fabricated and the lamellar structure was obtained in SDS-rich region. Here. respectively. (Tang et al..442 Ionic Liquids: Theory. especially in imidazolium ILs. 2009a). (Zhao et al.. Supramolecular structures based on the host networks in ionic liquids Generally. it has been found that supramolecular networks exist in pure ILs. hexylpyridinium tetrafluoroborate. 85. clear solution. the [C4mim][PF6] gels formed by the gelators may be used as electrolytes in electrochemical devices. where the mean minimum concentrations were found to be less than 2 wt% (Figure 13). Thus. New Approaches that IL is in favor of the formation of surfactant vesicle phase. vesicles and emulsion transformations at 30. 2009a) investigated the phase behavior of ternary system which was composed of [C16mim]Cl. where passed gel. Marangoni and his coworkers (Singh et al. (2009). (Tan et al. Schematic illustration of gelation of [C4mim][PF6] and the POM image of a [C4mim][PF6] gel formed in the presence of 2 wt% of BODM (magnification: 1000).. Zhao et al. Leclercq & Schmitzer. 4. 2009) reported the formation of spontaneous vesicle in the binary mixture of SDS and an IL amphiphile. Fig. which displayed reversible thermal transformation from fibrous assemblies to vesicles. SDS and water. Properties. 2009) reported that the gelation of [C4mim][PF6] were induced by the self-assembly of gelators. Tang et al. 2005). However.. 2004.

the above two-dimensional organization may evolve to three-dimensional structures through the chains of imidazolium rings (Figure 14B). 4. 2009a). 2004.. it depends on the geometry of anion and the nature of the imidazolium residues. Fuller et al.. followed by H(4) and H(5) of the imidazolium cation and sometimes by the proton of the α-carbon on nitrogen. Leclercq & Schmitzer. 14. Golovanov et al. and found that a perfect alternation of electron-rich and electron-poor ring can maximize the π-π stacking.. which are mostly electrostatic in nature. π-π stacking interactions among imidazolium rings. suitable to small and spherical anions with symmetric cations. These hydrogen bonds. Furthermore.. .Supramolecular Structures in the Presence of Ionic Liquids 443 organisation of ILs and some of the organisations observed in pure ILs in order to raise the interesting in exploring how the supramolecular structure of ILs affect the formation of supermolecules and supramolecular assemblies.(A) and three-dimensional (B) supramolecular structures of imidazolium ILs. 2000). Recently. 1998.N’-diaromatic diimidazolium cations. 2009b) synthesized N. C-H···π interactions and combination of these interactions) between the cations and the anions can also lead to the formation of the supramolecular network. In some cases.1 Supramolecular networks in ionic liquids 4.2 angstrom. 2004. which indicates the existence of an extended network of cations and anions connected together by hydrogen bonding (Figure 14A) (Dupont. (Leclercq et al. C-H···X bond angles between 100º and 180º). 2004. 2009a). 2006. Holbrey et al. π-π stacking. came from an overview of X-ray analyses results (Choudhury et al. Gordon et al. The unimeric unit is always constituted by one imidazolium cation surrounded by at least three anions and each anion is surrounded by at least three imidazolium cations. anions with phenyl residues (such as TPhB−) can interact with imidazolium cations via CH···π interactions and form a supramolecular framework (Dupont et al.. Leclercq & Schmitzer. Simplified two. For example. 2005. 2003). Dupont et al. which include electron-rich (aromatic) and electron-poor (imidazolium) rings. The strongest hydrogen bond always involves the most acidic H(2) of imidazolium ring.1. With respect to the specific number of anions/cations that surround the cation/anion... other interactions (such as electrostatic interactions.. Saha et al. 2005. Reprinted from Leclercq & Schmitzer (2009a). Leclercq et al.. 2000.1 Supramolecular structures in solid state A typical supramolecular model for imidazolium ILs in solid state (Dupont. Besides hydrogen bonding. and a relatively weak C-H···π interactions through the methyl group and the π system of the imidazolium ring can also be found in 1-alkyl-3- Fig. are weak to moderate (H···X bond lengths > 2. 1994.

Dupont (Dupont. .. electrostatic interactions are important in the construction of the extended networks (Leclercq et al. where the spherical anions are accommodated as one-dimentional chains. 2008).. 15. where I represents the imidazolium cation and X represents anion.. (B) Photograph and (C) fluorescent micrograph (λex = 514 nm) of an ionic network fiber prepared from 2P2+:H2TPP4−. 2007. This structural pattern also rests with the geometry of anion and the nature of the imidazolium residues. Fig. New Approaches methylimidazolium salts. in some special confined circumstances.444 Ionic Liquids: Theory. (A) Schematic diagram of the formation of a supramolecular ionic network and the molecular structures of the corresponding units. Sha et al. who is short of hydrogen band. Reprinted from Wathier & Grinstaff (2008) and Craig (2009). π-π stacking interactions and C-H···π interactions. such as tetrabutylammonium trifluoromethanesulfonate. This molecular arrangement can form channels. Recently. 2009). Therefore. 2004) proposed that the best description for the imidazolium salts in the solid state is [IxXx-n]n+[Ix-nXx]n−. Properties. As for other ILs. these weak interactions may be strengthened. such as the hollow interiors in multi-walled carbon nanotubs and the nanospace between graphite walls. Particularly. resulting in high-melting-point crystals of imidazolium ILs (Chen et al.

2002) and large-angle X-ray scattering experiment (Kanzaki et al.10.. Fukuda et al. As the length of the alkyl chain increases... 2009). Talaty et al. Wang & Voth. other ILs (such as N-alkyl-N-methylpyrrolidinium ILs (Fujii et al. Furthermore. 2009a). the ordered structure still exists. 2003). the porphyrins retained their fluorescence properties (Figure 15C). X-ray reflectivity experiment (Carmichael et al. 2007). 2006). Talaty et al. small-angle X-ray diffraction analysis (Bradley et al. Raman (Katayanagi et al. the nonpolar domains become larger and more connected. Furthermore.. In other words....1. This concept is supported by the results of IR (Dieter et al. 2009).. in a manner analogous to microphase separation (Lopes & Padua. this suggests that the above-mentioned nanodomains are built up by the aggregation of neutral alkyl chains surrounded by charges. Thus. the supramolecular structures observed in crystal are reserved in liquid state (Dupont. in particular those found in ILs. 1988. 2004.. the long-range order is lost. Although Fujii et al... which has a viscosity of about 1. NMR (Mele et al.. Besides imidazolium ILs. 2003). When EDTA4− was replaced by para-tetracarboxy-5.15. 2006). While the 2P2+:H2TPP4− IL was heated to 160 ºC.. the result of the XRD experiment also reflected that the size of the inhomogeneous structures is proportional to the length of the alkyl chain (Triolo et al. . suggested the presence of polar domains that are formed by the head groups of the cations and anions. thus suggesting the potential utility in sensors. might provide an interesting. 2005). an IL with a viscosity of ca. fluorescent spectra (Hu & Margulis. Thus. etc.. 2006.3-dialkylimidazolium ILs have analogous structural patterns in the solid and liquid phases. where the charge-charge interaction rather than the hydrogen bonding plays an essential role. 2004. Shigeto & Hamaguchi. 2008)) have also order structures in liquid state. whose uniform spatial distribution is determined by the strong electrostatic interactions (Triolo et al. 2004).20-tetraphenyl-21H. 2008) prepared an IL with ionic networks using a phosphonium dication (P2+) and a tetraanion.. Several MD simulations (Lopes & Padua. 2004). Raman spectra (Iwata et al. 2008b) found that the liquid structure of [C2mim][Tf2N] IL is significantly different from its layered crystal structure. (Fujii et al. 2006). 4. 2008a. 2009a). the results of X-ray diffraction (XRD) experiment (Triolo et al. ethylenediaminetetraacetate (EDTA4−) (Figure 15A). Leclercq & Schmitzer. 2007. 2006. Urahata & Ribeiro..23H-porphine. 2004. indicating that 1.. 2006). Within the fiber. 2001). 2007). 2004. 2007). a fiber could be hand-pulled from the liquid (Figure 15B). 2003..2 Supramolecular structures in liquid phase When ILs are transformed from crystal to liquid state. 2007) and optical Kerr Effect spectra (Xiao et al. but longrange Coulomb interactions between cations and anions in ILs are maintained (Dupont. 106 Pa·s at 25 ºC was obtained.. Ozawa et al. femtosecond solvation dynamics study (Adhikari et al. especially the work of Lopes and Padua (Lopes & Padua.. and complementary strategy for the formation of supramolecular structures (Craig. Recently. 2006). It is the long-range Coulomb interactions in ILs that can lead to longer spatial correlations than those in comparable classic van der Waals organic liquids (Cang et al.. Leclercq & Schmitzer. Hardacre et al. the above work suggests that ionic networks formed from effective noncoordinating ionic pairs. and of nonpolar domains that are formed by the alkyl groups in 1-alkyl-3methylimidazolium ILs (Cn ≥ C4). neutron diffraction analysis (Deetlefs et al. 2007) of 1-alkyl-3-methylimidazolium ILs also suggested the presence of heterogeneous structures.Supramolecular Structures in the Presence of Ionic Liquids 445 Wathier and Grinstaff (Wathier & Grinstaff. useful.2×104 Pa·s. H2TPP4− (Figure 15A). and cause swelling of the ionic network.

. In the former.. 2005). while the latter build from (anti)parallel stacking of the alkyl chains through van der Waals force. 1996. New Approaches there will be a competition between the interactions of a given solute with those two regions (Blesic et al. the Fig. In addition. 1999. Zhou & Antonietti. If an anion has a long alkyl chain. (Rebelo et al. can be applied (Bowlas et al. the long alkyl chains on the imidazolium ring are not necessary for the formation of LC (Mukai et al. 16.. 1997. consisting of interdigitated bilayers. Therefore. De Roche et al. smaller spheres and larger plates are triflate anions and imidazolium moieties. This supramolecular structure can be considered as the result of the alternate assembling of ionic layers and van der Waals layers.. 2007) suggested that a nonpolar solute (e. 2004. dark cylinders are the oxidized ones.. Reprinted from Yazaki et al.. 2009a). Generally. and schematic image of a nanostructured liquid crystal consisting of ionic and π-conjugated moieties (bottom): blank cylinders are neutral phenylterthiophene moieties.. Hardacre et al. water) will interact with the polar domains. Lin & Vasam.. ... while a dipolar or associative solutes (e. 2005b. Moreover. Up to now. Holbrey & Seddon.. 2002. Lee et al. (2008a). the ionic head groups interact with the counterions through Coulomb force.1. 1996.g. most of the found LC structures of imidazolium ILs are smectic A phase. Li et al.3 Thermotropic liquid crystal phase of ionic liquids As for imidazolium ILs with long alkyl chains (Cn ≥ C12). n-hexane) will interact preferentially with the nonpolar domains. 2008. the temperature range for LCs can be adjusted by altering counter anion and the length of alkyl chain. some metal complex anion... Lee et al. liquid crystal (LC) phase often appears in the course of increasing temperature (Bowlas et al. respectively. Properties. 2000. 2001.g. Molecular structure of 1-methylimidazolium ILs containing phenylterthiophene moiety (up). 4. 2004). Lee et al. 2003. Rebelo et al. 2004).. Bradley et al. such as PdCl4− and CuCl4−. this kind of heterogeneous structure of ILs will make the solubility and reactivity of solutes in ILs obviously different from those in the normal molecular solvents.446 Ionic Liquids: Theory. Getsis & Mudring.

. the synthesized compounds in columnar LC state were highly anisotropic ion-conductive in one-dimension (Yoshio et al. 2005. The structure of imidazolium ionic LCs is much simplex..Supramolecular Structures in the Presence of Ionic Liquids 447 hydrogen bonds between the H-atoms of imidazolium cations and anions are important in the formation and stabilization of ionic layers (Lee et al. Yoshio et al.. 2004. 2008a). 2000. 2007). unlike conventional redox-active conjugated polymers and liquid crystals (Yazaki et al. 2004.. Yoshio et al. leading to the formation of twodimensional ion-conductive channels between hole transport layers (Figure 16) (Yazaki et al.. 2008a) synthesized a new ILs with a 1-methylimidazolium group as an ion-conductive part and π-conjugated phenylterthiophene moiety related to the electronic charge transport (Figure 16). 2008b.. Yasuda et al. which makes its application in many fields confined. 2010. Yoshio et al. In experiment.... In order to resolve this problem..... Recently. 2006. Yazaki et al. 2008b). Fig. Lee et al... much effective effort has been made (Goossens et al. Kumar & Pal. and information at the nanometer level. Zhang et al. containing an L-glutamic acid moiety and bis(alkyloxy)phenyl groups (Figure 17). which would potentially be used as an on-off switch of ions (Figure 17) (Yazaki et al. Yazaki et al.. Kato et al. the IL exhibited electrochromism in the LC state without a liquid electrolyte layer. 2006. Recently. Yoshio et al.. Consequently.. 1997)... 2004. Yoshizawa et al.. 2007) and tunable feasible adjustment of LC properties by altering counter anions (Yoshio et al. Pal & Kumar. 2006. This LC would be applied to various electronic devices such as light-emitting electrochemical cells as well as the electrochromic devices. Yoshio et al.. They observed the appearance of a hexagonal columnar LC structure in 1-methylimidazolium ILs with tri-alkoxy substituted phenyl groups. In its smectic A phase. 2006. 2008b. Yazaki et al. Yoshio et al. 2010.. 2007. resulting in the oxidation of the π-conjugated moieties (Yazaki et al. 2007. Yoshio et al. especially the work of Kato and collaborators (Yasuda et al. and schematic illustration of an ideal on–off switch of ion conduction using the structural change from columnar to micellar cubic LC structures (right). the ionic and the π-conjugated moieties were nanosegregated. 2008d). 2007). Reprinted from Yazaki et al. 2008a). 2010.. 2010. Lee et al. 2004.. 2008b) prepared two new 1methylimidazolium-based ionic LCs. Kato and collaborators (Yazaki et al.. 2008a). 2004. (2008b). which would be useful for transportation of ions. 2004. 2006. Seo et al. 2008.. Yazaki et al. Besides a wide temperature range of LC phase (Yoshio et al. 2007). . Yoshio et al. Yoshio et al. The functionalization of imidazolium is a useful method for the application of imidazolium ionic LCs. 2006. 2007).. attached to the nitrogen atom (Yoshio et al. a class of LC mesogers. Yoshio et al.. 17.. Yoshio et al. 2004.. Molecular structures of 1-methylimidazolium ILs containing an L-glutamic acid moiety and bis(alkyloxy)phenyl groups (left). Yoshio et al. The ionic conductivities and LC structures of the obtained 1-methylimidazolium ILs could be conveniently adjusted by anions.... (Yazaki et al.. energy. the holes were injected from the anode and transported into the hole transport layers consisting of phenylterthiophene moieties (Figure 16).

2001. much evidence indicated that some of the supramolecular networks can be reserved when ILs are mixed with other materials and inclusion-type structures are formed.. rather than with hydrogen atoms within the imidazolium. 2001. For example. 2000) postulated that “wet” ILs may not be regarded as homogeneous solvents. Arkas et al.. 2008) further indicated that the ions of [C4mim][BF4] IL are selectively coordinated by individual water molecules. Cruz et al. 2001) considered that water molecules absorbed from the air by 1alkyl-3-methylimidazolium ILs are mostly in the “free” (not self-associated) state. quaternary ammonium (Alami et al. (Moreno et al. conductivity.448 Ionic Liquids: Theory... Schroder et al. but the ionic network is largely unperturbed at low water content.. 2001. (Takamuku et al. Neve et al. Through the research based on attenuated total reflectance IR spectroscopy. 1996. 2004). 1997). Najdanovic-Visak et al. In order to explain the large differences in the effect of water on the diffusion coefficient for neutral and for ionic species in imidazolium IL media. Sauer et al. 2009). 2004). neat imidazolium ILs have supramolecular framework. highly ordered smectic phases (the smectic E phase and the uncommon smectic T phase).. 4. dithiolium (Artzner et al. quaternary phosphonium (Abdallah et al. 2005.. Takamuku et al.1 Inclusion of water in ionic liquids Because ILs can absorbed significant amount of water from the atmosphere and trivial water is difficult to be removed. (Zhang et al. 2001.2 Inclusion phenomenon of guest compounds in the ionic liquid network As the above description. Gowda et al. Compton et al. such as polarity.. up to now. the behaviors of tri-alkyl-methyl-ammonium ionic LCs may be fine-tuned further to well defined hydrophobic thickness corresponding to uneven numbers of mean alkyl carbons. 2002. 2009). Mele et al. Chen et al. (Schroder et al.. by the use of simple binary liquid mixtures (Pott & Meleard.. viscosity.. with the change of alkyl chain length and counter anions. 4... It is also found that water is not homogenously mixed with [C2mim][BF4] IL at low water content (Zhang et al.. 2009). via hydrogen bond of type X−···HOH···X−. 2002.. Seddon et al. 2009). Mathevet et al. (Mele et al. Two important phenomena should be especially noticed. 2000. Later. Tittarelli et al. 2003) found that the H(2). smectic A phases. Based on the MD simulations and NMR experiment. via hydrogen bond. 1999. Neve et al. Properties. some of them have several kinds of liquid-crystalline structures.. 2009). H(4) and H(5) within the imidazolium ring could interact with water molecules via hydrogen bond of type C-H···O at very low water content by NMR spectroscopy through intermolecular nuclear Overhauser enhancements on [C4mim][BF4] IL. 2008) have also been explored. 2008c). (Cammarata et al. New Approaches Besides imidazolium ionic LCs. Cammarata et al. Taubert. 2008c) found that water molecules tend to interact with the anion moiety of ILs first. 1993... 1997.2. which is further confirmed by the most recent work of Takamuku et al. The existence of water in ILs may affect many of their physical and chemical properties. Recently... 2003... most of which act as bridge between anions (X−). Widegren et al. but have to be considered as “nano-structured” with polar and non-polar regions. Mele et al. and reactivity as well as solvation and solubility properties (Brown et al. Cui et al.. Lu et al. 1998. 2009. Firstly. 2005). 2000.. 1997) and guanidinium ILs (Kim et al... 2000. 2000. Zhang et al. .. Furthermore.. Secondly.. water becomes the most common impurity in ILs (Huddleston et al.. Pott & Meleard.. Cammarata et al. such as BF4− and PF6−. and hexagonal columnar phases were observed in the pyrrolidinium ILs (Goossens et al.... other thermotropic ionic LCs based on pyridinium (Bowlas et al. Gordon et al. pyrrolidinium (Goossens et al. 2005. 2000.

at low water content. while the concentration of IL is too low to be detected in the upper layer. 2010). forming a tube-like structure with a rectangular cross-section around the cations of ILs. when both dipole and quadrupole moments are present in an aromatic compound. 2006) draw the similar conclusion from the crystal structure of [C2mim][NTf2]·C6H6 (Figure 18B). they have an antagonistic effect.5C6H6 by cooling the lower phase of the [C1mim][PF6]−C6H6 system to room temperature. a typical supramolecular structure for imidazolium ILs in solid state. it was found that the immiscibility gap became smaller when the polarity of substituted benzenes increased and their molecular size decreased (Shiflett & Yokozeki. 2009). Holbrey et al. 2010) further found that the presence of a . 2005) further indicated that the addition of benzene to [C1mim][PF6] leads to an expansion of the cation−cation contacts through the neutron diffraction study on the [C1mim][PF6]−C6H6 mixtures. immiscibility with excess aromatic solvents. the water could be regarded as guest included in the supramolecular framework of imidazolium ILs. 2003) obtained crystalline [C1mim][PF6]·0. The formation of clathrate phases could be regarded as an example of the organization of guest molecules in the pre-organised host network.e.. no direct hydrogen bonds between cations and anions were observed in the crystal structure of [1. 2007. The crystal structure of the clathrate (Figure 18A) shows that there is a three-dimensional array of hydrogen-bonded cations and anions. the formed structure has to allow for a higher proportion of benzene molecules.Supramolecular Structures in the Presence of Ionic Liquids 449 In addition..2 Inclusion of aromatic compounds in ionic liquids After mixing of some imidazolium ILs with excess of aromatic hydrocarbons. (Kowsari et al... and non-stoichiometric (but reproducible) compositions..2. 2000) and so on. alternating cation-anion layers are observed with the first-shell anions interacting with the ring hydrogens while the cations interact with the ring electrons.. 2002.3-dibenzylimidazolium]Br·H2O. Clavier et al. From another point of view. separations of aromatics from hydrocarbons (Arce et al. (Deetlefs et al. (Lachwa et al. Alavi et al. Later.. This three-dimensional framework results in the formation of “channels” along the (001) direction of the crystal lattice in which benzene molecules are included by a staggered π−π ”sandwich” between two imidazolium cations. However. DeCastro et al. Selvan et al. biphasic mixtures are obtained. such liquid clathrates or IL-biphases have been used in the fields of organic syntheses (Boxwell et al. 2009. but water molecules connected anions and cations in the supramolecular framework (Leclercq et al. which exhibits the characteristics of typical liquid clathrates. Recently. suggesting benzene intercalation into the structure as found in the solid. Moreover. The lower layer is IL-rich phase. Lachwa et al. Shiflett et al. through the MD study of its congruent melting. Benzene is also found to be homogeneously distributed throughout the IL with no evidence of micellar formation. water molecules were included in the crystal lattice.... Surette et al. 2009c). 4. the existing states of water molecules in the liquid and crystal phases support the hypothesis of polar and non-polar regions of the supramolecular network. 1996). i. Thus. (Holbrey et al.. 2002).. low viscosity (relative to the initial neat ILs). 2000.. around the benzene molecule. Shiflett & Niehaus. polymerization (Csihony et al. The incorporation of benzene is found to displace the anions with approximate three benzenes replacing each anion. reducing the solubility in the IL (Shimizu et al. In other words. 2008. However... Up to now. With respect to the inclusion crystal [C2mim][NTf2]·C6H6. 2008. Deetlefs et al.

5C6H6 (A) and [C2mim][NTf2]·C6H6 (B). Huang et al. Gutowski & Maginn.. 2008) and (bio)macromolecules (Dupont. pyridinium (Christie et al. Pickett. 2004. 2004.. 2007. even nanoparticles (Dupont.. Properties. Reprinted from Holbrey et al. Lee et al. 1991) and so forth (Gaudet et al. The co-crystal structure of [C2mim][TfO] and [Bu4N][TfO] (Figure 19) could be described as a supramolecular framework formed by C2mim+ and TfO− through hydrogen bonding.. Packing patterns in the crystal structures of [C1mim][PF6]·0. Besides imidazolium ILs.2.3 Co-crystals of ionic liquids It has been reported that imidazolium ILs are able to form co-crystals with quaternary ammonium ILs with same anions (Leclercq et al. 2006. but increases the mean-square displacements of both cations and anions compared to pure liquid [C2mim][NTf2]. Dupont. may act as guests included in the supramolecular host framework of ILs. 2008). Weingartner. (2003) and Lachwa et al. other ILs based on quaternary ammonium (Coleman et al. 18. Leclercq & Schmitzer. 1985). in which all Bu4N+ are trapped (Leclercq et al... 2008). e... 2009a). 2007. 1988) can also form liquid/solid clathrates with aromatic molecules.. New Approaches Fig. Besides the above three kinds of molecules. 2008). 2008. gas molecules (such as CO2) (Costantini et al. 5. Feher et al. showing that second shell ionic associations are weakened. g. 2005. 2009a. . 4. Leclercq & Schmitzer. This phenomenon may be considered to be another example of the inclusion of guest molecules in the supramolecular host network. (2006). Effects of ionic liquids on the formation of supramolecular structures ILs can not only participate directly in the formation of supramolecular systems. 2009).450 Ionic Liquids: Theory. [C2mim][TfO] with [tetrabutylammonium][TfO] ([Bu4N][TfO]) (Leclercq et al.. 2004. in which suitable anions are important. but also influence the formation of various supramolecular structures. 1990.. stoichiometric number of benzene molecules does not affect the nearest neighbor ionic association between [C2mim]+ and [NTf2]−.

2007). were good solvents for PRs.Supramolecular Structures in the Presence of Ionic Liquids 451 Fig. 2006) used ILs as new solvents for PR. 19. Reprinted from Leclercq et al. Dai et al. F127 may squeeze [C4mim][PF6] molecules out from β-CD and thread themselves instead into the cavity of β-CD and finally precipitate with more CDs being stacked (Figure 20). Interestingly.1 Effects of ionic liquids on the formation of polyrotaxanes and polypseudorotaxanes Polyrotaxanes (PRs) and polypseudorotaxanes (PPRs) formed by CDs in the presence of ILs have been studied. they are being used in the extraction of metal ions. (Dai et al. This discovery was applied in the preparation of IL-containing slide-ring gels (SR gels). obtaining the distribution coefficient as . 2008). using a devised “non-drying” technique accompanied by solvent exchange. will finally be included inside β-CD. Samitsu et al. 1999) used the system dicyclohexano-18-crown-6 (DCH18C6) -[R1R2mim][NTf2]/[PF6] to extract Sr2+. However. regardless of their cations. such as chlorides or bromides. amino acid and so on. They found that halogen-containing ILs. (2008). At higher ethanol concentration. F127 or [C4mim][PF6]. though coulomb interactions between the ionic (liquid) components and hydrogen bonding are important (Gjikaj et al. which are supramolecular networks of PR swollen with ILs. can be controlled by ethanol amount around the initially β-CD/[C4mim][PF6] ICs. 5. because of the influence of ILs to the system of crown ethers. consisting of α-CD and poly (ethylene glycol). 5.. It was found that not only the PO segments but also many EO segments are included by β-CD molecules in the PPRs.2 Effects of ionic liquids on the formation of the supramolecular structures in the extraction systems based on crown ethers No significant close contacts are observed between ILs and crown ethers based on the study of co-crystallisation of imidazolium based salts with 18-crown-6 (18C6). A kind of PPRs were prepared by supramolecular self-assembly of β-CDs threaded onto the triblock copolymers (Pluronic F127) in [C4mim][PF6] with two different manners (Jing et al. which one.. (Samitsu et al... For the first time. (A) View of the local assembly around a tetrabutylammonium cation (Bu4N+) and (B) space-filled view of the co-crystal of [C2mim][TfO] and [Bu4N][TfO].

New Approaches Fig. Properties. The traditional crown ether. they found that H2βDA18C6 provides a remarkably high performance for Sr2+ extraction into [C2mim][Tf2N] due to a cooperative “intramolecular” interaction when compared with the “intermolecular” synergy extraction system of the mixture of HPMBP and DBzDA18C6. 2010. (Shimojo et al. Recently. To increase the extraction efficiency of metal ions.13-diaza-18-crown6 (DBzDA18C6). can extract metal ions efficiently. 2005). were added into the system due to the formation of a synergistic adduct (Stepinski et al. more and more systems involved ILs and crown ethers were investigated (Chun et al.. the transfer of Sr2+ into [C2mim][Tf2N] proceeds via the proton exchange reaction. However. Stepinski et al..... Shimojo et al. 2000. These results discovered that as the alkyl group in the ILs was elongated. Xu et al. The extraction process can be easily tailored by varying the substituting groups in the imidazolium cation and the counter anions.. metal ions are not easy to be stripped. Schematic representation of the inclusion choice between F127 and [C4mim][PF6]. The distribution is not only related to the concentration and the hydrophobicity of crown ethers.. but the extraction selectivity increased. Reprinted from Jing et al. The two protons from protonated H2βDA18C6 were released to extract Sr2+. The influence of γ-radiation on the IL [C4mim][PF6] and [C4mim][Tf2N] during extraction of Sr2+ by DCH18C6 was studied . Sr2+ was extracted by a novel extractant β-diketone-substituted diaza-18-crown-6 (H2βDA18C6). 2007. 2009. 2001. 2009). They discovered a strong dependence of selectivity on the type of ILs.. a series of N-alkyl aza-18-crown-6 ethers were synthesized (Luo et al. Langmaier et al. The magnitude of the synergistic enhancement is shown to depend on the alkyl chain length of the ILs [Cnmim][Tf2N] cation. In order to overcome this disadvantage. the extraction efficiency decreased.452 Ionic Liquids: Theory. (2007). 2009) reported the first study on the “intramolecular” synergistic extraction of a metal ion in an IL-based system. with the effect diminishing as the cation hydrophobicity increases until for [C10mim][Tf2N]. for example DCH18C6. Visser et al. Okamura et al. such as TBP.N’-dibenzyl-4. 2004a). 20. 2010. Because ILs are usually used in the separation of radioactive nuclides and the radiation effect on ILs for the extraction of metal ions is important.. but also to the composition of the aqueous phase. Nockemann et al. high as 104. In succession.. the additives. By compared with 1phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP) and N. These crown ethers in ILs were investigated as recyclable extractants for separation of Sr2+ and Cs+ from aqueous solutions.

Ishida et al. Besides. Dietz & Dzielawa... The selectivity of these TSILs is dependent on the structure of substituents on the imidazolium ring. 2009. anion exchange (Jensen et al. and modifying their lipophilicity. 2002. Owing to the molecular-recognition ability.. 2007). Luo et al. 2003. Due to the competition between H+ and Sr2+. 2001) (TSILs) contain specific functionality covalently incorporated within one of the ionic components of the IL. for example the thermal decomposition temperatures (Tdec) of the ILs containing crowned cations are generally 80-100 ºC higher than those of the ILs having crowned anions. The mechanism of ILs-crown ethers system for metal ions extraction has been studied extensively. This can be attributed to the coulombic repulsion from the covalently attached imidazolium cation. 1999.. 2006) synthesized a new class of TSILs based on the covalent attachment of imidazolium cations to a monoaza-crown ether fragment. 2010a). Dietz et al. limited solubility of ionic species in nonionic organic solvents is the main problem and the toxicity of free crown ethers makes them unsuitable for industrial use. Task Specific ILs (Bates et al. The ILs functionalized by the crown ether may display potential utility in catalytic application as well as in separation and electrochemical sensing. There are several kinds of mechanisms: cation exchange (Dai et al. 2008. Dietz et al. The Sr2+ partitioning in irradiated [C4mim][PF6] decreases as the absorption dose increases. The stereochemistry of crown ethers can also affect the mechanism.. It is also reported that the stability of cesium complexed with 18C6 in ILs is affected by the nature of both cation and anion of ILs (Vendilo et al. (Ishida et al. 2005). 2008. 2004. stability constants of metal ion complexes with crown ethers in IL aqueous solutions were obtained (Popov et al. A series of novel ILs comprising crown-ether functionalities in cations or anions (crowned ILs) were prepared and characterized (Liu et al. In the conventional organic solvents extractions.. the predominant mode of partitioning changes from ionexchange involving the cationic portion of the IL to conventional neutral nitrato complex extraction (Dietz et al.. The “crowned” ILs obtain their selectivity through their ability to fine-tune and reorganize their crown ether structure changing their number and type of donor atoms. 2007) and the solubilization of the ILs [Cnmim][Tf2N] by the presence of crown ether was studied (Rickert et al. Therefore.. Popov et al.Supramolecular Structures in the Presence of Ionic Liquids 453 (Yuan et al. The oxygen lone pairs had a potential as Lewis-basic and/or hydrogen-accepting functionality.. Visser et al. the “crowned” IL-crown ether as a functional group to functionalized IL was performed for a liquid/liquid extraction of metal ions (Park et al. the complex stability is important for the extraction process (Vendilo et al... 2005). Hirayama et al... These TSILs exhibited lower extraction efficiency than the IL extraction systems using DCH18C6 or N-octylaza-18-crown-6 as extractant. 2001. 2005). (Dietz et al.. 2009). 2006.. This is the result of the formation of acid during the irradiation of [C4mim][PF6]... the extraction efficiency decreased and can be recovered by simple washing the irradiated [C4mim][PF6] with water. 2003).. Vendilo et al.. (Luo et al. DCH18C6 have five . Park et al. the enantiometic imidazolium cations could differently sense the chirality of the europium complexes. The irradiation of IL influences greatly on this system. appending ionizable groups. typically within the cation.The physical properties of different functionalized ILs were different. 2008) studied the DCH18C6 stereochemistry influence the mode of sodium ion transfer from acidic nitrate media into ILs. the hydrophobicity of the IL cation increase (from n=5 to n=10 in [Cnmim][Tf2N]). 2006) and molecular-recognition ability (Ishida et al.. Moreover. Liu et al. 2003). 2010b). mechanism of multiple distribution (Dietz & Stepinski. 2007)... 2004) designed and synthesized novel imidazolium-based ILs with a pseudo crown-ether moiety. By changing the ILs.

rising aqueous acidity is accompanied by increasing sodium extraction. Properties. 2004)... the positive form of amino acids is complexed by the crown ether and the complex is extracted in the IL phase (CardaBroch et al. 2003). In contrast.5) into [C4mim][PF6] with DCH18C6 (Smirnova et al. 2002. and cis-trans (ct) isomers of DCH18C6. i. 2007).0 (Lys and Arg at pH 1. trans-syn-trans (tst). Shimojo et al. the process of extracting can be controlled by the isomers of extractants. Amino acids are hydrophilic and therefore difficult compounds for conventional solvent extraction. Pyridinocalix[4]arene showed a high extraction ability and selectivity for Ag+ in five different metal ions (Ag+. 2006a. 2003). While using conventional organic solvents the protein transfer was negligibly small. 21.5-4. The most hydrophilic amino acids such as Gly were extracted as efficiently as the less hydrophilic ones. Ala. trans-syntrans (tst). van Rantwijk et al. trans-anti-trans (tat) and cis-trans (ct) (Figure 21). for the trans isomers. As a result. which usually occurs when cationic or anionic extractants are used.5-5. Reprinted from Dietz et al. rising nitric acid concentration is eventually accompanied by steeply falling values of the sodium distribution ratio. 2006b) investigated a hydroxyl-groupcontaining IL with DCH18C6 was capable of quantitative partitioning of heme protein cytochrome c (Cyt-c) via supramolecular complexation and that the resulting Cyt-cDCH18C6 complex acts as a homogeneous biocatalyst in ILs. A change from a cis to a trans isomer of DCH18C6 alters the predominant mode of sodium ion portioning into [C10mim][Tf2N] from ion-exchange to neutral complex extraction. [C8mim][PF6]. Shimojo et al. Gly. Sieffert & Wipff.. ILs and crown ethers used in biochemistry have also been a field of increasing interest and importance (Kragl et al. cis-anti-cis (cac). trans-anti-trans (tat). however. ILs enabled quantitative recovery of amino acids and eliminated emulsion formation. Cu2+. Amino acids were not soluble in IL. Amino acids Trp. Leu were efficiently extracted from aqueous solution as pH 1. For the cis isomers. Fig. New Approaches isomers. (Shimojo & Goto. by adding a crown ether to the IL phase. Extractants comprised calixarene part in IL systems were also investigated (Shimojo & Goto. 2004a. cis-anti-cis (cac). (Shimojo et al. cis-syn-cis (csc). The partitioning of a protein into ILs is controllable on the basis of hydrophobicity and type of the functional groups of ILs. Molecular structures of the cis-syn-cis (csc). Co2+ and Ni2+). consistent with partitioning of a neutral sodium nitrato-crown ether complex.454 Ionic Liquids: Theory... This is the first report showing protein extraction into ILs. (2008). Shimojo et al. This was originated the crown ether-mediated exchange of a sodium ion for a hydronium ion in a DCH18C6H3O+ adduct. Zn2+. 2004b) studied the extraction of metal ions by a calix[4]arene-bearing pyridine in a typical IL..e.. This compound transfers Ag+ into IL . Compared to the conventional organic solvents.

the less solubilities of BOBCalixC6 in the corresponding ILs and the higher distribution coefficients because the less hydrophobic imidazolium cations have higher ion-exchange capability. Li et al. Luo et al. In the LM+ complexes. A dual extraction mechanism for extraction Cs+ by the BPC6/[Cnmim][Tf2N] system. can decrease the loss of ILs by 24%. Chen.Supramolecular Structures in the Presence of Ionic Liquids 455 phases via a cation-exchange mechanism and form a stable 1:1 complex with Ag+. 2004b) extracted Cs2+ into [Cnmim][Tf2N] using calix[4]arenebis(tert-octylbenzo-crown-6) (BOBCalixC6) as an extractant by an ion-exchange mechanism.. The LCs+ complex and L ligand behave differently and they are better solvated by the IL than by chloroform.. a sacrificial cation exchanger. 2006. They are adsorbed at the chloroform interface and adopt well-defined amphiphilic orientations. Tsuda et al.. while in the [C4mim][PF6]-humid IL. found that the bis(2propyloxy)calix[4]crown-6 (BPC6)/[Cnmim][Tf2N] system was highly efficient to remove Cs+ from aqueous solution. There is more intersolvent mixing with the IL than with chloroform especially the water-in-oil content. At the IL interface. 2009a). 2008. there is some excess of C4mim + over Tf2N−. Supramolecular gelation in IL could be used in many fields. membranes. Rogers et al.. 2007. The shorter alkyl chain of the ILs. Fig. (Luo et al. polymer electrolytes. .. 2006a. MD study of the interfacial behavior in the Cs+ and Na+ extraction by a calix[4]arene-crown6 host (L) into ILs [C4mim][Tf2N] and [C4mim][PF6] demonstrated the IL forms a biphasic system with water (Sieffert & Wipff. There are two aspects about effects of ILs on these supermolecules. or gate dielectrics for organic transistors. The addition of NaBPh4. ion exchange take a partial role. 2004. Reprinted from Xu et al. These results provide a number of arguments explaining the specificity and efficiency of IL based extraction systems.... 2010). Very recently. 2009. Park et al. Compared with the classical molecular solvent (chloroform). 2009b. they are poorly attracted. the first salvation shell of the “naked” M+ ions is composed of solvent anions only. 2008. 2009). as a result. They discovered that the importance of humidity.. In the [C4mim][PF6]-dry as in the [C4mim][Tf2N] liquid. Paramasivam et al. b). The structures and characteristics of nanohybrids or nanocomposites or self-organized nanotubes can be changed by the assistant of ILs (Gopalan et al. Wu et al. A dual extraction mechanism. exchange of BPC6-Cs+ complex and Cs+ by Cnmim+ was mentioned (shown in Figure 22) (Xu et al. 2005. Xu et al.. In the aqueous phase. Recently.3 Effects of ionic liquids on other supermolecules The primary role of IL is to maintain good solvent conditions over a very wide temperature range for supramolecular ion gel (Mohmeyer et al. it comprises from one to three solvent anions and about four H2O molecules.. The comparison of [C4mim][Tf2N] and [C4mim][PF6] of the dry versus humid form of the latter one. calixarene comprising crown ethers have been extensively studied in the IL-extraction system (Chen & Hussey. 5. the cation is shielded from solvent but still somewhat interacts with a solvent anion in the dry ILs and with water in the humid IL. 2009a. (2010). such as actuators. 2006). 22. Luo et al. 2007. Noro et al. much longer times are needed to “equilibrate” IL systems..

. Zhang et al. and decreased Nagg. Li et al. Evans et al. 2006. (Moniruzzaman et al. 2009b. These observations implied an overall unfavorable micellization process when the IL was present. 2007. New Approaches which influence the system individually or jointly. Zheng et al. 2007b) reported that [C4mim][PF6] and [C4mim][BF4] participated in the TX-100 micellar phases. Relative studies on the aggregation of nonionic surfactants in ILs have been reported (Evans et al.. 2006. It was found that the addition of 30 wt % [C4mim][BF4] resulted in decreased micellar size. Inoue & Misono. 1982. It suggested that when the concentration of [C4mim]Br was below 1. 2007). microemulsions. ILs also influence the aggregation behavior of Pluronic polymers (Dey et al. 2009b. 2008e). 2000) and can form different supramolecular networks from other solvents (Pedireddi et al.. Later. 2004. the micellization was found to be entropy driving (He et al. (Behera et al. The micelle formation is caused by the solvophobic interactions between the hydrocarbon chains of the surfactant molecules just like hydrophobic interactions in aqueous medium. Wu et al. P104 micelles and [C4mim]Br clusters coexisted in the system (Figure 23).. ILs participated in the formation of micelles. 2008). Wang et al. Behera et al. Lei et al. Properties. ILs have also been found to influence the formation of micelles as co-surfactant. 2007a. liquid crystals and vesicles. cation-π and/or π-π stacking interactions (Gopalan et al. . which can result in electrostatic interactions. 2009). 2008. The sensitivity of molecularly imprinted polymers (MIPs) can be improved by ILmediated method (Booker et al. b. 2007. Patrascu et al. In addition. In addition. Li et al. 2009a. 2009. Park et al. Zheng et al. Ueki et al... 2009a. 2008a.. 2009. IL also influenced the formation of the supramolecular assemblies as solvents and co-solvents. Gao et al. all of which were unchanged in aqueous [C4mim][PF6]-TX-100 systems because of the low solubility of [C4mim][PF6].. 2009. Park et al... 5.. 2009). 2004.. 2007a. 2009). 2008) reported the formation of reverse micelles in [C8mim][Tf2N] comprising sodium bis(2-ethyl-1-hexyl) sulfosuccinate (AOT) as surfactant with 1-hexanol as a cosurfactant. Sifaoui et al. 2006.. 2007) studied the effect of [C4mim]Br on the aggregation behavior of PEOPPO-PEO P104 aqueous solution. Ma et al... Modaressi et al. Beyaz et al. The micelle formation of surfactants.... 2009a. 2007a.. Fletcher & Pandey. 2008b.. The other is that self-assemby of ILs influence the supermolecules (Gutel et al..4 Effects of ionic liquids on the formation of supramolecular assemblies As mentioned above.. the concentration-dependent dual role of the ILs in altering physicochemical properties of ionic surfactant (SDS. ILs are also used to synthesize other supramolecular host compounds (Scott et al. He et al. (Zheng et al. b).. Xu et al.. there were P104 micelles in the aqueous solution with [C4mim]Br embedding to the micellar core.232 mol/L. 2009.. CTAB) was demonstrated (Behera & Pandey.. 2007a.. increased cmc.. amphiphilic Pluronic polymers were found to be able to form well defined micelles in IL. It is found that ILs acted as a metal salt at low concentrations and participated in the micellar phase with increasing [C4mim][PF6] which led to a considerable decrease in the microfluidity of SDS micelles (Behera & Pandey. One is that ILs affect the supermolecules because of the anions and cations of ILs and aromatic structures. while above this concentration. Wang et al. 2007). 2003).. This formation of aqueous droplets in the IL is attributed to the hydrophobic effects between the AOT tails and the long hydrocarbon chain of IL and the strong tendency of the AOT head group to interact with water.....456 Ionic Liquids: Theory.. 2006. such as SDS and Brij-35 in ILs ([C4mim]Cl and [C4mim][PF6]) was first studied by Armstrong and his coworkers (Anderson et al. Zhang et al. 2005). 1983b. Wu et al. Masahiro et al.. Behera et al.

Atkin & Warr. microemulsions. 1987.. b.. for example... which was formed by β. many studies on the formation of liquid crystals in ILs are reported (Araos & Warr. 2007).. Conclusions In conclusion. It is . Zhao et al. 2005. The formation of liquid crystal in ILs was firstly reported by Evans and co-workers (Evans et al. CnEm.. 2008a. Wang et al. They attributed the additional V2 phase in the P123-EAN system to the higher affinity for the hydrophobic PPO blocks to EAN than to water.e.. 2007. micelles. cucurbit[n]urils and calixarenes). 2009b). 2008a) reported the aggregation of Pluronic P123 in EAN. which might reduce the effective area of the solvophilic headgroup and increase the volume of the solvophobic part.e.γ-distearoylphosphotidylcholine (DSPC) in EAN. Greaves et al. Since then. Tamuralis et al. 23. and can participate the constructing of supramolecular assemblies (i. 6.. Zhang et al. (2007). Besides. 1983a) in 1983. which was similar to those observed in H2O or [C4mim][PF6] systems.. and so on.Supramolecular Structures in the Presence of Ionic Liquids 457 Fig. formed lyotropic liquid crystals in EAN and it was found that longer alkyl chains were necessary to drive the formation of liquid crystalline. cyclodextrins. The aggregation behavior of [C16mim]Cl in EAN was also investigated and an additional V2 (reverse bicontinuous cubic) phase was identified when comparing such a phase behavior with that of the [C16mim]Cl/H2O binary system (Zhao et al. Schematic illustration of the different types of complexes formed when [C4mim]Br was added to 5% Pluronic P104 aqueous solution. Reprinted from Zheng et al. 2007a. ILs can affect the formation of supramolecular structures. the formation of the supramolecular structures in the extraction systems based on crown ethers. (Zhang et al. ILs can act as guests to form supermolecules with several kinds of host molecules (i. 2009b). lyotropic LCs. 2004. 2005. Nonionic surfactants. Zhang et al. the formation of polyrotaxanes and polypseudorotaxanes. Atkin & Warr. suggesting that a rich pattern of “solvophobic” selfassembly (Araos & Warr. vesicles and gels)..

However. However. Moreover. Otherwise. In ILs. this field has not been mentioned. the effect of the supramolecular structures of ILs on the formation of supramolecular assemblies is another valuable subject. more and more interesting phenomena and important results will be obtained. these fields of ILs are just beginning to be noticed. which makes the system more complicated. how do the host molecules interact with guest molecules. we noticed that water plays the key role in the formation of IL based microemulsions. New Approaches also noticed that imidazolium ILs have a three-dimensional supramolecular network with polar and non-polar regions. 90206020 and 20871009). the investigation of ILs will encounter a new chance and challenge. Recently.3-dimethylimidazolium cation alkyl poly-(oxyethyleneglycol) ethers . Acknowledgements This work was supported by the National Natural Science Foundation of China (Grant No. Therefore. the host-guest interaction usually takes place in aqueous solution. in the reference. In addition. 8. For example. which can be used as powerful supramolecular receptors. two cases would happen. ILs are not pure. With the development of the exploration in these fields. because trivial water is difficult to be removed and could be included in the supramolecular framework of imidazolium ILs. If the hydrophobic interactions between oil and surfactant are stronger than the interactions between IL and oils. and how do ILs affect the interaction? These are two interesting and challenging subjects. liquid clathrate can be destroyed and O/IL microemulsions form. A small quantity of water can lead to great change in the phase diagram of IL/TX-100/oil ternary systems. when the surfactant is added into the IL/oil mixture. This supramolecular structure may also affect the formation of supramolecular assemblies. Properties. Abbreviations 18C6 1P10X ACE AdCO2− AOT BF4− BOBCalixC6 BPC6 Bu4N+ C3Br Calix-S4 Calix-S6 CBn CD(s) cmc Cndmim+ CnEm 18-crown-6 tri-n-decylmethylphosphonium chloride and bromide affinity capillary electrophoresis adamantylcarboxylate anion sodium bis(2-ethyl-1-hexyl) sulfosuccinate tetrafluoroborate anion calix[4]arene-bis(tert-octylbenzo-crown-6) bis(2-propyloxy)calix[4]crown-6 tetrabutylammonium cation propyl-(2-hydroxyethyl)-dimethyl-ammonium bromide 4-sulfonatocalix[4]arene 4-sulfonatocalix[6]arene cucurbit[n]uril cyclodextrin(s) critical micelle concentration 1-alkyl-2. a new state would exist instead of O/IL microemulsions. Now. Thus. when ILs are used as solvents.458 Ionic Liquids: Theory. 7. how will the supramolecular structures of ILs themselves affect the formation of supramolecular assemblies.

γ-distearoylphosphotidylcholine dodecyltrimethylammonium bromide ethylammonium nitrate freeze-fracturing electron microscopy β-diketone-substituted diaza-18-crown-6 hydroxypropyl-β-CD 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone hydroxypropyl-α-CD hydroxypropyl-γ-CD inclusion complex ionic liquid(s) isothermal titration calorimetry liquid crystal(s) lower critical solution temperature molecular dynamics nonafluorobutanesulfonate anion oil-in-IL oil-in-water oxyethylene tosylate anion propylammonium formate hexafluorophosphate anion poly(NIPAAM-co-β-CD Methacrylate) small-angle neutron scattering small-angle X-ray scattering sodium dodecylsulfate trans-anti-trans tetrabutylammonium perfluorooctanoate thermal decomposition temperatures bis(trifluoromethylsulfonyl)imide anion trifluoromethanesulfonate anion heptakis-(2.Supramolecular Structures in the Presence of Ionic Liquids 459 [CnH2n+1mim][CmH2m+1SO3] Cnmim+ (CN)2N− CnOSO3− CnPy+ Cnvim+ DBzDA18C6 DCH18C6 [DDA][NO3] DLS DM-β-CD DPPC DSPC DTAB EAN FFEM H2βDA18C6 HP-β-CD HPMBP HP-α-CD HP-γ-CD IC IL(s) ITC LC(s) LCST MD NfO− O/IL O/W OE OTos− PAF PF6− PNCM SANS SAXS SDS tat TBPFO Tdec Tf2N− TfO− TM-β-CD TPhB− TSIL 1-alkyl-3-methylimidazolium alkylsulfonate 1-alkyl-3-methylimidazolium cation dicyanimide anion alkylsulfate anion 1-alkylpyridinium cation 1-alkyl-3-vinylimidazolium cation N. N’-dibenzyl-4.3. 13-diaza-18-crown-6 dicyclohexano-18-crown-6 didecyl-dimethylammonium nitrate dynamic light scattering heptakis-(2.6-tri-O-methyl)-β-CD tetraphenylborate anion task specific ionic liquid .6-di-O-methyl)-β-CD L-dipalmitoylphosphatidylcholine β.

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