The role of building-block metrics in the halogen-bonding-driven self-assembly of calixarenes, inorganic salts and diiodoperfluoroalkanes.

Halogen bonding effectively co-operates with ion-ion interactions in determining the supramolecular structure of three-component heteromeric crystals comprising of calix[4]arenes, inorganic salts and diiodoperfluoroalkanes. The subtle interplay between these two types of interactions, as well as the influence of the valence of the metal ion, the "size" of the calixarene platform and the length of the perfluorocarbon module on the stoichiometry and overall supramolecular organisation of the ternary supramolecular architectures is discussed. The relevance to the overall packing of the size matching between the pitches along the cationic and anionic sub-lattices is also discussed.