The structure-directing or template effect has been invoked several times for ionic liquids to explain the different outcome in material synthesis, namely, different scaffolds or geometrical arrangements with varying ionic liquids. It is obvious to assume that such an effect can originate from the most likely complex microstructure, being present within the ionic liquid itself. In that regard, ionic liquids have already been shown to undergo a nanosegregation into polar and nonpolar phases, which is commonly known and denoted as microheterogeneity. In order to provide detailed insight on the molecular level and to understand the effects rising from this structuring, we performed molecular dynamics simulations on selected very simple model systems composed of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, considering ethyl, butyl, hexyl, and octyl side chains attached to the cations, mixed with either n-dodecanol or n-butanol. By analyzing snapshots of the simulation boxes and calculating spatial distribution functions, we can visualize that with increasing side chains, the systems show considerable nanosegregation into polar and nonpolar domains. Combined angular and distance distribution functions show that in case of the nanosegregating systems the side chains of the cations are preferentially arranged in a parallel fashion, which indicates a micelle-like structure for the ionic liquids. The alcohol molecules participate in and are, therefore, influenced by this microheterogeneity. It can be shown that in the case of the short IL alkyl side chains, the self-aggregation of the nonpolar units of the alcohols is much stronger, while for the long chain cations, the nonpolar entities of the alcohols are most often connected to the nonpolar units of the ionic liquids. Using our domain analysis tool, we can quantify these observations by tracking the number, size, and shape of the polar and nonpolar entities present in the different investigated systems. The aforementioned combined angular-distance distribution functions reveal a structure-directing effect of the ionic liquids on the alcohol molecules within our simple model systems. The ionic liquids act as template and order the alcohol molecules according to their own structure, resulting in a parallel alignment of the alkyl side chains of the alcohols and ionic liquid cations, with both polar groups being at the same side. These observations show that the microheterogeneous structure of ionic liquids can indeed be applied to order substrates with respect to each other or, for example, to catalysts in a predetermined fashion, opening new possibilities for explaining or enhancing selectivities of chemical reactions in ionic liquids.

To gain a deeper understanding of the TiCl4 solvation effects in multi-component ionic liquids, we performed ab initio molecular dynamics simulations of 1-butyl-3-methylimidazolium [C4C1Im]+, tetrafluoroborate [BF4]−, chloride [Cl]− both with and without water and titanium tetrachloride TiCl4. Complex interactions between cations and anions are observed in all investigated systems. By further addition of water and TiCl4 this complex interaction network is extended. Observations of the radial distribution functions and number integrals show that water and TiCl4 not only compete with each other to interact mainly with [Cl]−, which strongly influences the cation-[BF4]− interaction, but also interact with each other, which leads to the fact that in certain systems the cation-anion interaction is enhanced. Further investigations of the Voronoi polyhedra analysis have demonstrated that water has a greater impact on the nanosegregated system than TiCl4 which is also due to the fact of the shear amount of water relative to all other components and its higher mobility compared to TiCl4. Overall, the polar network of the IL mixture collapses by including water and TiCl4. In the case of [Cl]− chloride enters the water continuum, while [BF4]− remains largely unaffected, which deeply affects the interaction of the ionic liquid (IL) network.

With the aid of ab initio molecular dynamics simulations, we investigate an ionic liquid (IL) mixture composed of three components 1-butyl-3-methylimidazolium [C 4 C 1 Im] + , tetrafluoroborate [BF 4 ] − , and chloride [Cl] − without and with water. In the pure IL mixture, we observe an already complex network of interactions between cations and anions, and addition of water to the system even extends the complexity. Observed number integrals show that the coordination number between cations and anions is reduced in the system with water compared to that in the pure system. Further studies show that the Coulombic network of the strongly coordinating anion [Cl] − is disturbed by water, while that of the weakly coordinating anion [BF 4 ] − is not. These observations can also be confirmed by the Voronoi polyhedra analysis, which shows that the polar network of microheterogeneous IL collapses by the introduction of water. Hydrogen-acceptor interactions revealed that the [Cl] − anions are transferred from being situated in the IL to the water continuum, while [BF 4 ] − is almost unperturbed; these effects mainly influence the interplay of the ionic liquid network.