conjugated molecules. Aza-annulative π-extension (AAPE) reactions are particularly appealing for their capacity to efficiently create complex fused aza-arene structures on conjugated molecules. These reactions integrate imine moieties as an acceptor-units into conjugated systems (Figure ), giving rise to donor-acceptor systems with unique material properties. As depicted in Figure , such an iron-catalyzed AAPE reaction ideally uses easily accessible carbonyl compounds, which are conveniently generated by 5 the oxidation of aromatic hydrocarbons 4 or condensation , through direct C-H bond activation in the presence of a nitrogen source and an alkyne. This methodology is exemplified in its application to pentacenequinone and quinacridone , precursors in the manufacture of classical organic semiconductors and pigments, enabling the cost-effective production of novel electronic materials (Figure ). However, challenges persist in iron-catalyzed C-H activation. Despite the development of over a 10 decade , issues like the limited range of directing groups and the competition from oxidative C-H coupling with carbon nucleophiles, employed as bases for deprotonative C-H activation, remain formidable obstacles to efficient iron-catalyzed AAPE reactions.