Hybrid iodoperfluoroalkane-ferrocene supramolecular arrays: the shortest contacts iodine forms with nitrogen atoms and unsaturated moieties

α,ω-Diiodoperfluoralkanes self-assemble in solution and in the solid phase with (S)-(−)-N,N-dimethyl-1-ferrocenylethylamine. The formed adducts have been characterized by DSC, IR, Raman, 1H and 19F NMR techniques. Single crystal X-ray analysis of one of the obtained adducts shows that perfluorinated and organometallic modules alternate giving rise to infinite one-dimensional (1D) chains. The interacting modules are connected through strong n-type halogen bondings, involving nitrogen and iodine atoms, and weak π-type halogen bondings, involving Cp rings and iodine atoms. Both interactions are the shortest reported to now in their respective classes. Theoretical calculations have been performed to quantify the observed π-type halogen bonding. For the first time a metallocene-perfluorocarbon (PFC) hybrid material is described.