Straightforward access to tetraboron-doped acenes: B4-pentacenes and B4S2-heptacene donor-acceptor dyads.

A rational synthesis using in situ-generated 1,2-bis(dibromoboryl)benzene intermediates enables the stepwise synthesis of fourfold boron-doped B4-pentacenes in preparatively useful yields, mitigating unselective cross-condensations. This approach grants access to previously elusive silylated, borylated, and fluorinated Bn-acenes. Subsequent SNAr functionalization affords a B4S2-heptacene donor-acceptor dyad with promising optoelectronic applications.