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

alpha,omega-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, H-1 and F-19 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 pi-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 pi-type halogen bonding. For the first time a metallocene-perfluorocarbon (PFC) hybrid material is described. (C) 2004 Elsevier B.V. All rights reserved.