<i>N</i>‑Directed Two-Fold Bromoboration\nof Diynes Enables Access to Brominated BN-Embedded PAHs

<i>N</i>-directed 2-fold bromoboration reactions\nof diynes\nwith BBr<sub>3</sub> have been developed, allowing the access to novel\ninternally BN-doped polycyclic aromatic hydrocarbons from readily\navailable precursors under mild conditions. Computational investigations\nidentified three potential reaction mechanisms, each involving either\nBBr<sub>3</sub> or [BBr<sub>4</sub>]<sup>−</sup>, with low\nactivation barriers (<i>ΔG</i><sup><i>‡</i></sup> < 16 kcal/mol) for all pathways. The resulting brominated\nproducts can be further functionalized through various cross-coupling\nprotocols, enabling the synthesis of highly luminescent emitters with\nquantum yield exceeding 90.