Dual‐Phosphorus, Dual‐Nitrogen‐Embedded Corannulene: Synthesis, Structure, and Electronic Coupling

Bowl‐shaped π‐conjugated molecules incorporating heteroatoms provide unique opportunities to explore structure–property relationships arising from molecular curvature and solid‐state organization. Here, we report the synthesis and characterization of P2N2‐TBC , the first corannulene‐based heterobuckybowl incorporating two phosphorus and two nitrogen atoms. P2N2‐TBC was synthesized through a stepwise strategy that enables sequential incorporation of phosphorus units into a rigid benzo‐fused framework. Single‐crystal X‐ray diffraction analysis revealed a curved bowl geometry and the formation of distinct cis and trans stereoisomers in the solid state. Detailed structural analysis showed that these stereochemical differences lead to markedly different packing motifs. Crystal‐structure‐based electronic coupling calculations further demonstrated that cis ‐ P2N2‐TBC exhibits directional electronic coupling associated with columnar packing, whereas trans ‐ P2N2‐TBC displays more evenly distributed but moderately sized couplings across multiple directions. These results highlight how stereochemical variation within a single P2N2‐embedded bowl‐shaped π system influences solid‐state organization and electronic interactions, and expand the structural and functional landscape of heterobuckybowls.