Bamboo-like Chained Cavities and Other Halogen-Bonded Complexes from Tetrahaloethynyl Cavitands with Simple Ditopic Halogen Bond Acceptors

Halogen bonding provides a useful complement to hydrogen bonding and metal-coordination as a tool for organizing supramolecular systems. Resorcinarenes, tetrameric bowl-shaped cavitands, have been previously shown to function as efficient scaffolds for generating dimeric capsules in both solution and solid-phase, and complicated one-, two-, and three-dimensional frameworks in the solid phase. Tetrahaloethynyl resorcinarenes (bromide and iodide) position the halogen atoms in a very promising crown-like orientation for acting as organizing halogen-bond donors to help build capsules and higher-order networks. Symmetric divalent halogen bond acceptors including bipyridines, 1,4-dioxane, and 1,4-diazabicyclo[2.2.2]octane are very promising halogen bond accepting partners for creating these systems. This report describes the complex structures arising from combining these various systems including self-included dimers, herringbone-packed architectures enclosing medium (186 angstrom(3)) cavities, and a very intriguing bamboo-like one-dimensional rod with large (683 angstrom(3)) cavities between adjacent dimeric units. These various structures, all organized through host-host, host-acceptor, and host solvent interactions highlight the emergent complexity of these types of complexes. As halogen bonds are weaker than hydrogen bonds, the resulting architectures are harder to predict, and these results provide additional insight into the parameters requiring consideration when designing crystalline supramolecular systems using halogen-bonds as the core organizing principle.