Bicyclic BODIPY-Submonoazaporphyrin Hybrids via a Catalyst-Free SNAr Strategy: Coexisting Local Aromaticity and Global Antiaromaticity with Broad NIR-II Absorption

A series of bicyclic BODIPY-submonoazaporphyrin hybrids were efficiently constructed via a catalyst-free SNAr strategy, exhibiting excellent chemical stability. These hybrids exhibit a unique coexistence of local 14π aromaticity and global 28π antiaromaticity, which was unambiguously verified by NMR spectroscopy and theoretical calculations. Moreover, they show remarkably broad UV–vis–NIR absorption spanning the range of 300–1400 nm (NIR-II) and rich redox properties, thereby providing an effective strategy for designing novel porphyrinoids with tunable aromaticity as stable NIR functional materials.