Halogen bond is emerging as a significant driving force for supramolecular self-assembly, and has aroused great interest during the last two decades. Among the diverse halogen-bonding donors, we take notice of the ability of 1,4-diiodotetrafluorobenzene (1,4-DITFB) to co-crystallize with diverse halogen-bonding acceptors in the range from neutral Lewis bases (nitrogen-containing compounds, N-oxides, chalcogenides, aromatic hydrocarbons and organometallic complexes) to anions (halide ions, thio/selenocyanate ions and tetrahedral oxyanions), leading to a great variety of supramolecular architectures such as discrete assemblies, 1D infinite chain and 2D/3D networks. Some of them act as promising functional materials (for instance, fluorescence, phosphorescence, optical waveguide, laser, nonlinear optics, dielectric and magnetism), and soft materials (e.g. liquid crystal and supramolecular gels). Here we focus on the supramolecular structures of multicomponent complexes and their related physicochemical properties, highlight representative examples, and show clearly the main directions which remain to be developed and improved in this area. From the point of view of crystal engineering and supramolecular chemistry, the complexes summarized here should give helpful information for further design and investigation on the elusive category of halogen-bonding supramolecular functional materials.

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Efficient ultraviolet organic microcrystal lasers were demonstrated based on bulky diarylfluorene dimers with a fully coplanar conformation.