Cationic π-conjugated organic molecules have broad applications in materials science as next-generation organic materials. The annulative alkyne-insertion π-extension (AAIPEX) strategy has emerged as a promising synthetic approach for the rapid synthesis of cationic polycyclic heteroaromatic compounds (cPHACs) in a single step. The AAIPEX reaction provides a synthetic shortcut to achieve complex organic molecules from simple (hetero)arene templates and alkynes as π-extending partners, which would otherwise be difficult to achieve using traditional methods. In general, a step-economic AAIPEX protocol proceeds C-H activation of unfunctionalized heteroarene templates, followed by alkyne insertion-annulation to furnish cPHACs. In this Feature Article, recent progress in the AAIPEX strategy to construct cPHACs is described along with brief illustrations of the resulting cPHACs in luminescence-related applications.
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