Chiral Diazatriptycene Exhibiting Acid‐Induced Ternary Circularly Polarized Luminescence Switching and Crystal Morphology Changes

Doubly N‐doped triptycene 2,6‐diazatriptycene 1 was synthesized as the first example of triptycene‐bearing intrinsic chirality in its core. The resolved enantiomers exhibited an acid‐induced ternary circularly polarized luminescence (CPL) switching behavior, enabling on/off and +/– control, with a dissymmetry factor (glum) of approximately 10–3. Density functional theory calculations indicated that these ternary CPL changes were derived from modulation of through‐space conjugation within the triptycene skeleton. In addition, single‐crystal X‐ray analysis of 1 and the salt 1•(TfOH)n revealed the presence of herringbone arrangements, trimer clusters, chiral porous tubes, and 2D charge‐segregated array structures. These results demonstrate that precise change of the molecular assembly can be achieved using N‐doped chiral triptycene facilitated by ionic hydrogen bonding and donor‐acceptor π‐π stacking.