A Chiral Molecular Cage Comprising Diethynylallenes and N‐Heterotriangulenes for Enantioselective Recognition

Chirality, a characteristic tool of molecular recognition in nature, is often a complement of redox active systems. Scientists, in their eagerness to mimic such sophistication, have designed numerous chiral systems based on molecular entities with cavities, such as macrocycles and cages. In an attempt to combine chirality and redox‐active species, in this contribution we report the synthesis and detailed characterization of a chiral shape‐persistent molecular cage based on the combination of enantiopure diethynylallenes and electron‐rich bridged triarylamines, also known as N‐heterotriangulenes. Its ability for chiral recognition in solution was revealed through UV/vis titrations with enantiopure helicenes. It's a match! A novel shape‐persistent chiral cage constituting two N‐heterotriangulene lids and three bis(diethynylallene) branches is reported, along with UV/vis complexation studies with both charged and neutral helicenes. Enantioselective discrimination was observed, which, in combination with the redox behavior of the host, makes the system appealing as a model for dual sensors with both chiral and electronic modulation.