The functionalization of polycyclic aromatic hydrocarbons (PAHs) via B ! NL ewis pair formation offers an opportunity to judiciously fine-tune the structural features and optoelectronic properties,tosuit the demands of applications in organic electronic devices,b ioimaging,a nd as sensitizers for singlet oxygen generation. We demonstrate that the N-directed electrophilic borylation of 2,6-di(pyrid-2-yl)anthracene offers access to linearly extended acene derivatives Py-BR (R = Et, Ph, C 6 F 5 ). In comparison to indeno-fused 9,10-diphenylanthracene,t he formal "BN for CC" replacement in Py-BR selectively lowers the LUMO,r esulting in am uchr educed HOMO-LUMO gap.A ne ven more extended conjugated system with seven six-membered rings in ar ow (Qu-BEt)i s obtained by borylation of 2,6-di(quinolin-8-yl)anthracene. Fluorinated Py-BPf shows particularly advantageous properties,i ncluding relatively lower-lying HOMO and LUMO levels,s trong yellow-green fluorescence,a nd effective singlet oxygen sensitization, while resisting self-sensitized conversion to its endoperoxide.

No abstract