Triazacoronene Derivatives with Three peri‐Benzopyrano Extensions: Synthesis, Structure, and Properties

New π‐extended triazacoronene derivatives containing three peri‐benzopyrano extensions were successfully synthesized through tandem triflic acid catalyzed threefold Pictet–Spengler cyclization and K2CO3‐catalyzed ipso‐aromatic substitution in one pot. The structure was verified by X‐ray diffraction analysis and was found to form a sandwich‐type π trimer in the crystalline state. The π‐extended triazacoronenes showed reasonable solubility, high thermal stability, and remarkably repeatable electroluminescent emissions. π‐Extended triazacoronenes are synthesized by a one‐pot process involving tandem triflic acid (TfOH)‐catalyzed threefold Pictet–Spengler cyclization and K2CO3‐catalyzed ipso‐aromatic substitution. NMP = N‐methylpyrrolidone.