We have described a conceptually novel approach where cation binding occurs thanks to coordination by a K.2.2.2. like podand and anion binding is secured by iodotetrafluorobenzene residues covalently linked to the podand. The X-ray structure of the solid NaI/podand adduct prove the ability of the podand to simultaneously recognize the iodide through halogen bonding and the sodium through the oxygen and nitrogen atoms of the K 2.2.2 analogue. The driving force for the self-assembly is provided by a cooperativity of cationic endo-recognition and anionic exo-recognition processes. Anion binding in the liquid and gas phase will also be described.