Bridging of Cove Regions: A Strategy for Realizing Persistently Chiral Double Heterohelicenes with Attractive Luminescent Properties.

The racemization of chiral organic compounds is a common chemical phenomenon. However, it often poses configurational-stability issues to the application of this class of compounds. Achieving chiral organic compounds without the risk of racemization is fascinating, but it is challenging due to a lack of strategies. Here, we reveal the cove-regions bridging strategy for achieving persistently chiral multi-helicenes (incapable of racemization), based on the synthesized proof-of-concept double hetero[4]helicenes featuring macrocycle structures with a small 3D cavity. Additionally, we demonstrate that the strategy is also effective in tuning the electronic structures of multi-helicenes, resulting in a conversion from luminescence silence into thermally activated delayed fluorescence (TADF) for the present system. Furthermore, red circularly polarized TADF based on small double [4]helicene systems is achieved for the first time using this strategy. The disclosed cove-regions bridging strategy provides an opportunity to modulate the electronic structures and luminescent properties of multi-helicenes without concern for racemization, thus significantly enhancing the structural and property diversity of multi-helicenes for various applications.