2,3 : 6,7‐Naphthalenediimide‐Based Chiral Triangular Macrocycle: Self‐Assembled Helix, Outer π‐Surface Directed Co‐Assembly and Circularly Polarized Luminescence

Abstract Here, we report the synthesis and self‐assembly of a novel chiral 2,3 : 6,7‐naphthalenediimide‐based triangular macrocycle (NDI‐Δ) and its chiroptical properties. The enantiomeric NDI‐Δ 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 exhibits unique chiroptical properties and self‐assembly modes. The NDI‐Δ shows circularly polarized luminescence (CPL) in solution and can self‐assemble into helical structures with the inversion of CPL signal and the enhancement of | g lum |. Moreover, the NDI‐Δ 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‐Δ through π‐π stacking and C−H π interactions. This work provides a critical example for the 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.