Genesis of Complex Polyiodide Networks: Insights on the Blue Box/I−/I2 Ternary System

The Stoddart’s blue box (BB) (cyclobis(paraquat-p-phenylene))/iodide binary system was recently demonstrated to give rise to porous three-dimensional networks which can hardly be classified as common XOF-type materials (X = M, C, S, i.e., metal, covalent, or supramolecular organic frameworks), leading to the definition of permutable organized frameworks (POFs). The ternary BB/iodide/iodine system was reported to generate pentaiodide-based structures constituted by the most complex interlocked polyiodides so far isolated (up to an infinite supramolecular pseudopolyrotaxane with a poly[3]catenane axle). The missing link, i.e., the XRD structure of the BB/triiodide complex, is herein reported: structural similarities and novel Raman evidence, opening perspectives in the genesis of solid-state BB-based complex polyiodide networks from solution.