We report on the modification of the electric properties of the imidazolium-based [BMIM][NTf2] ionic liquid upon surface confinement in the sub-monolayer regime. Solid-like insulating nanostructures of [BMIM][NTf2] spontaneously form on a variety of insulating substrates, at odd with the liquid and conductive nature of the same substances in the bulk phase. A systematic spatially resolved investigation by atomic force microscopy of the morphological, mechanical and electrical properties of [BMIM][NTf2] nanostructures showed that this liquid substance rearranges into lamellar nanostructures with a high degree of vertical order and enhanced resistance to mechanical compressive stresses and very intense electric fields, denoting a solid-like character. The morphological and structural reorganization has a profound impact on the electric properties of supported [BMIM][NTf2] islands, which behave like insulator layers with a relative dielectric constant between 3 and 5, comparable to those of conventional ionic solids, and significantly smaller than those measured in the bulk ionic liquid. These results suggest that in the solid-like ordered domains confined either at surfaces or inside the pores of the nanoporous electrodes of photo-electrochemical devices, the ionic mobility and the overall electrical properties can be significantly perturbed with respect to the bulk liquid phase, which would likely influence the<br>performance of the devices.<br>
Cover Picture: Halogen‐Dependent Surface Confinement Governs Selective Alkane Functionalization to Olefins (Angew. Chem. Int. Ed. 18/2019)