In recent years, the number of non-aqueous solvents which mediate hydrocarbon-solvent interactions and promote the self-assembly of amphiphiles has been markedly increased by the reporting of over 30 ionic liquids which possess this previously unusual solvent characteristic. This new situation allows a different exploration of the molecular "solvophobic effect" and tests the current understanding of amphiphile self-assembly. Interestingly, both protic and aprotic ionic liquids support amphiphile self-assembly, indicating that it is not required for the solvents to be able to form a hydrogen bonded network. Here, the use of ionic liquids as amphiphile self-assembly media is reviewed, including micelle and liquid crystalline mesophase formation, their use as a solvent phase in microemulsions and emulsions, and the emerging field of nanostructured inorganic materials synthesis. Surfactants, lipids and block co-polymers are the focus amphiphile classes in this critical review (174 references).

The ability of ionic liquids (ILs) to support amphiphile self-assembly into a range of mesophase structures has been established as a widespread phenomenon. From the ILs evaluated as self-assembly media, the vast majority have supported some lyotropic liquid crystal phase formation. Many neat ionic liquids have been shown to segregate into polar and non-polar domains to form a nanostructured liquid. A very strong correlation between the nanostructure of the ionic liquid and its characteristics as an amphiphile self-assembly solvent has been found. In this review we discuss ionic liquids as amphiphile self-assembly media, and identify trends that can be used to distinguish which ionic liquids are likely to have good promotion properties as self-assembly media. In particular these trends focus on the nanostructure of neat ionic liquids, their solvent cohesive energy density, and the related solvophobic effect. We forecast that many more ILs will be identified as amphiphile self-assembly solvents in the future.