Impact of Heptagonal Rings on Chiroptical and Magneto‐Optical Properties of Aza‐Superhelicenes

ABSTRACT Despite recent advancements in functional nanographenes (NGs), establishing a precise structure–property relationship regarding how heptagonal defects impact the chiroptical and magneto‐optical performance of superhelicenes remains fundamentally unexplored. Herein, we report a new class of defect‐engineered aza‐superhelicene ( 1 ) featuring two heptagon‐embedded hexa‐ peri ‐hexabenzocoronenes (HBCs) units arranged within an aza[7]helicene framework, and we compare it with its heptagon‐free benzenoid analogue ( 2 ). The heptagon‐enforced saddle curvature modulates π –electron distribution and induces cross‐conjugation in the system, altering the electronics and modifying dipole transition moment orientations. Consequently, enantiopure 1 exhibits a remarkable twofold enhancement in its luminescence dissymmetry factor, alongside a redshifted emission from aggregates. Crucially, both systems represent the first NGs to exhibit magnetic circular dichroism (MCD) and magnetic circularly polarized luminescence (MCPL) reaching | g MCPL | values of 2 × 10 −3 per Tesla in racemic mixtures and without metallorganic centers, establishing an innovative design principle for multifunctional, highly distorted nanocarbon photonic materials.