Abstract: Polyiodide chemistry is among the first historically reported examples of supramolecular forces at work. To date, owing to the increasingly recognized role of halogen bonding and the incorporation of iodine-based components in several devices, it remains an active field of theoretical and applied research. Herein we re-examine azacyclophanes as a class of ligands for the stabilization of iodine-dense three-dimensional networks, showing how we devised novel possible strategies starting from literature material. The new set of azacyclophane ligands affords novel crystal structures possessing intriguing properties, which develop on a double layer. At a macroscopic level, the obtained networks possess a very high iodine packing density (less than 2 times more diluted than crystalline I₂): a simple parameter, I_N, is also introduced to quickly measure and compare iodine packing density in different crystals. On the microscopic level, the present study provides evidence about the ability of one of the ligands to act as a three-dimensional supramolecular mold for the template synthesis of the rarely bserved heptaiodide (I₇^-) anion. Therefore, we believe our approach and strategy might be relevant for crystal engineering purposes.

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DOI:10.3390/inorganics7040048