Surface-Induced Changes in the Thermochromic Transformation of an Ionic Liquid Cobalt Thiocyanate Complex.

We demonstrate that a thermodynamic complex equilibrium within an ionic liquid film can be significantly influenced by the presence of the liquid-vacuum interface. Using surface-sensitive X-ray photoelectron spectroscopy, we find that the temperature-driven transition from the blue-colored tetrahedral [Co(II) (NCS)4 ]2- to the red-colored octahedral [Co(II) (NCS)6 ]4- complex already occurs within the outermost nanometers at around +4 °C as compared with -25 °C in the bulk. This thermochromic transformation in the near-surface region goes along with a loss in preferential surface orientation of free [SCN]- anions and with a pronounced decrease in the complex density; both effects are attributed to the formation of a weakly bound solvation shell around the [Co(II) (NCS)6 ]4- anion, leading to an effective complex dilution. Our results are not only relevant for high-surface area thin film systems, such as in sensor and catalysis applications, but also shed light on the role of ionic liquid surfaces in particular and liquid surfaces in general.