Aza-dicyclopenta[a,g]naphthalenes: controllable seesaw-like emissive behavior and narrowband AIEgens

Abstract

Molecular motions significantly influence the emissive behavior and properties of organic fluorescent molecules. However, achieving controllable emission remains a major challenge for fluorophores. In the case of aggregation-induced emission luminogens (AIEgens), the desired properties of aggregated emission and narrowband spectrum demand molecular motion patterns that inherently oppose each other. A nitrogen-containing dicyclopenta[a,g]naphthalene scaffold was discovered as a controllable luminogenic structure through a highly efficient one-step intermolecular cascade reaction. By carefully balancing molecular motions and introducing additional nitrogen atoms into the skeleton, pyrrole-conjugated dicyclopenta[a,g]naphthalenes with aggregation-caused quenching (ACQ) could be transformed into dual-state emission luminogens (DSEgens). This transformation was achieved by incorporating an additional weak H-bond “lock.” Furthermore, the DSEgens could be converted into AIEgens with an exciting narrow full-width-at-half-maximum (FWHM, <50 nm) by methylation. This unprecedented discovery is attributed to the contribution of the weak H-bond “lock,” which overcomes the limitations of broad band emission in AIEgens caused by restrictions of intramolecular motion. Specific organelle probes were developed by replacing the methyl group of the onium product with different positioning groups. This study emphasizes the delicate balance of molecular motions in controlling luminescence and demonstrates a successful approach to designing organic luminogens with controllable emission and narrowband AIEgens.