Fluorous nanodroplets structurally confined in an organopalladium sphere.

The distinct properties of fluorous phases are practically useful for separation, purification, and reaction control in organic synthesis. Here, we report the formation of a liquid-like fluorous droplet, composed of 24 perfluoroalkyl chains confined in the interior of a 5-nanometer-sized, roughly spherical shell that spontaneously assembled in solution from 12 palladium ions and 24 bridging ligands. Crystallographic analysis confirmed the rigid shell framework and amorphous interior. Perfluoroalkanes can dissolve in this well-defined fluorous phase, whereas they can hardly dissolve in a surrounding polar organic solution, and their solubility (up to approximately eight perfluoroalkane molecules per spherical complex) can be finely controlled by tuning the length of perfluoroalkyl chains tethered to the shell.