Synthesis of a twisted azananographene featuring a diquinoxaline-fused pyrene

π-Extension from a diquinoxaline-fused pyrene led to a twisted azananographene (azaNG) exhibiting red emission. Although the azaNG was highly contorted, the electronic nature of the diquinoxaline-fused pyrene was confirmed to be retained, and thus it exhibited three-electron accepting ability as well as a low-lying LUMO level.