Hybrid calixarene/inorganic salt/diiodoperfluorocarbon supramolecular assemblies

1,3-Bis(alpha-picolyloxy)-p-tert-butylcalix[4]crown-5 in the cone conformation (2), 1,8-diiodoperfluorooctane or 1,6-diiodoperfluorohexane, and potassium iodide ternary mixtures undergo in solution self-sorting and afford crystalline "supramolecular salts". These hybrid materials consist of supercation [K+ subset of 2] and superanion [I-(CF2)(n)-I center dot center dot center dot I-center dot center dot center dot I-(CF2)(n)-I center dot center dot center dot I-center dot center dot center dot] (n = 6,8) components. In the supercations the potassium ion is embedded in the ionophoric pocket created by the heteroatoms present at the lower rim. In the superanions the iodide ions form infinite fluorous polyanionic chains as a result of a self-assembly process which relies on halogen bonding. Both cation encapsulation and anion-perfluorocarbon halogen bonding were detected in solution by H-1 and F-19 NMR, and in the gas phase by ESI MS.