Halogen bonding (XB) has demonstrated to be an effective tool for inducing the self-assembly of halo-perfluorocarbons (PFCs) with hydrocarbons and/or inorganic salts and obtaining new hybrid, crystalline materials, which contain long-chain PFCs. Here, we report the first examination of the surface of these crystals through Scanning Force Microscopy (SFM) techniques providing a new insight into their unusual structures. Our attention was focused on the ternary supramolecular complex 5 given by 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-hexadecafluoro-1,8-diiodooctane (4) with the cryptate Kryptofix^® 2.2.2. Ì KI 3 (formed by 4,7,13,16,21-24-hexaoxa-1,10-diazabicyclo[8,8,8]-hexacosane 1 and potassium iodide 2). The ternary system 5 crystallizes with trigonal symmetry in the  space group and forms large hexagonal or triangular thin plates having their largest faces perpendicular to the c crystallographic axis.

SFM techniques were employed to obtain structural and surface compositional information. The fundamental (001) surface, which is the largest in the crystal 5, was found to consist of large and narrow terraces, which expose the single PFC module 4, and the cryptate 3, respectively with the PFC module 4 thus covering the largest area.