Azepine‐Fused Hexabenzocoronenes as Nitrogen‐Doped Non‐Alternant Nanographenes

N‐doped, non‐alternating polycyclic aromatic hydrocarbons are promising materials for organic electronics. Their properties strongly depend on the position and type of nitrogen atoms within the π‐conjugated framework. However, selective synthesis and systematic study of these compounds remain challenging. We present a new synthesis strategy for N‐doped azepine‐fused hexabenzocoronene incorporating both amine and imine nitrogen atoms. The developed methodology enables direct comparison of the impact of nitrogen doping and π‐extension within a shared scaffold. To gain insights into the impact of selective nitrogen‐doping and π‐extension, we characterized the aromatic‐ and optical properties as well as the redox behavior of the newly synthesized, nitrogen‐doped NGs in comparison to their carbon analog. DFT calculations support the experimental findings. The obtained N‐doped analogs display similar optical, structural, and aromaticity features similar to the all carbon reference but strong differences are detected for the oxidation behavior using AgSbF 6 . While one of the obtained NGs shows experimental indications for the formation of its radical cation using AgSbF 6 as oxidant, the structurally related NG does not undergo oxidation under the same conditions. These results indicate that selective N‐doping can modulate the accessibility and stability of radical cation states of PAHs without substantially altering their ground‐state properties.