Halogen Bonding Mediated Hierarchical Supramolecular Chirality.

As a highly directional force, halogen bonds based on σ-holes have potential to manipulate supramolecular chirality and build functional chiral systems, which however are largely unexplored. In this work, we report the manipulation of supramolecular chirality in hierarchically self-assembled systems via intracomponent halogen bonds. Cholesteryl cyanostilbene conjugates and 1,3,5-trifluoro-2,4,6-triiodobenzene formed a C3 symmetrical supramolecular complex with ultrahigh binding affinity and binding constants at 1011 order of magnitude. The halogen bonded propeller geometries exhibited inversed chirality as well as chiroptical activity compared to the pristine helically orientated aggregates. Halogen bonds enabled the engineering of nanoarchitectures, affording supercoiled helical structures and highly aligned nanotubes. This work unveils the role of halogen bonds in controlling supramolecular chirality, establishing a protocol to build functional chiroptical materials from species containing σ-holes and halogenated domains.