Halogen-bonding of iodide salts with iodoperfluorocarbon results in the formation of a variety of networks. The use of these molecular ?legos? in the construction of highly interpenetrating networks is a function of cation used in supramolecular architecture formation. This talk will focus on the synthesis of halogen-bonded species using monoiodo- as well as diiodoperfluoroalkanes. The use of bulky cations for selective separation of fluorocarbon mixtures will also be discussed.