Abstract
<jats:p>Developing circularly polarized luminescent (CPL) organic emitters that simultaneously exhibit high emission efficiency and strong chiroptical activity remain a significant challenge. Herein, we report a computationally guided design strategy for donor-functionalized azahelicenes with enhanced CPL performance. By evaluating transition dipole moment parameters and predicted glum values, representative azahelicene candidates were identified, synthesized, and systematically investigated. Single-crystal analysis revealed that donor functionalization and structural locking play crucial roles in modulating helical geometry, molecular rigidity, and intermolecular packing. In solution, these azahelicenes exhibited efficient fluorescence and pronounced chiroptical responses, with |gabs| and |glum| values reaching the 10-2 level. TD-DFT calculations further elucidated the relationship between molecular structure, transition dipole orientation, and CPL activity. Moreover, one azahelicene derivative AzaICz-1 displayed reversible pH-responsive luminescence and chiroptical switching, accompanied by red-shifted emission spectra and slightly reduced g values after protonation. This work provides valuable insights into the rational design of high-performance and stimuli-responsive chiral luminescent azahelicenes.</jats:p>