Linear Extension of Anthracene via B←N Lewis Pair Formation: Effects on Optoelectronic Properties and Singlet O2 Sensitization.

Abstract

The functionalization of polycyclic aromatic hydrocarbons (PAHs) via B←N Lewis pair formation offers an opportunity to judiciously fine-tune the structural features and optoelectronic properties, to suit the demands of applications in organic electronic devices, bioimaging, and 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, C6 F5 ). In comparison to indeno-fused 9,10-diphenylanthracene, the formal "BN for CC" replacement in Py-BR selectively lowers the LUMO, resulting in a much reduced HOMO-LUMO gap. An even more extended conjugated system with seven six-membered rings in a row (Qu-BEt) is obtained by borylation of 2,6-di(quinolin-8-yl)anthracene. Fluorinated Py-BPf shows particularly advantageous properties, including relatively lower-lying HOMO and LUMO levels, strong yellow-green fluorescence, and effective singlet oxygen sensitization, while resisting self-sensitized conversion to its endoperoxide.