-Directed Two-Fold Bromoboration of Diynes Enables Access to Brominated BN-Embedded PAHs.

-directed 2-fold bromoboration reactions of diynes with BBr have been developed, allowing the access to novel internally BN-doped polycyclic aromatic hydrocarbons from readily available precursors under mild conditions. Computational investigations identified three potential reaction mechanisms, each involving either BBr or [BBr], with low activation barriers ( < 16 kcal/mol) for all pathways. The resulting brominated products can be further functionalized through various cross-coupling protocols, enabling the synthesis of highly luminescent emitters with quantum yield exceeding 90.