2,3:6,7‒Naphthalenediimide‐based Chiral Triangular Macrocycle: Self‐Assembled Helix, Outer π‐surface Directed Co‐assembly and Circularly Polarized Luminescence

Here, we report the synthesis and self‐assembly of a novel chiral 2,3:6,7‒naphthalenediimide‐based triangular macrocycle (NDI‐∆) and their chiroptical properties. The enantiomeric NDI‐∆ is synthesized by condensation of (RR) or (SS)‐trans‐1,2‐cyclohexanediamine and 2,3,6,7‐naphthalenetetracarboxylic 2,3:6,7‐dianhydride, in which the chirality of the macrocycles is controlled by the diamine. With the rigid outer π‐surface, the macrocycle showed unique chiroptical properties and self‐assembly modes. The NDI‐∆ showed circularly polarized luminescence (CPL) in solution and can self‐assemble into helical structures with the inversion of CPL signal and the enhancement of |glum|. Moreover, the NDI‐∆ has a tailored electron‐deficient outer π‐surface, which can co‐assemble with an electron‐rich anthracene (AN) to form an intermolecular charge transfer (CT) complex, generating a yellow‐green CT‐CPL. Crystal structure analysis confirms that AN is mounted on the outer surface of NDI‐∆ through π‐π stacking and C‐H···π interactions. This work provides a critical example for self‐assembly of macrocycles into helical structures and outer π‐surface directed CT complexes formation, opening up a new clue for designing chiral macrocycle‐based chiroptical materials.