Core extension of alkylene-encapsulated perylene bisimides

Abstract

Molecular engineering of perylene bisimides via long-axis covalent macrocyclic encapsulation and short-axis core-extension is presented. Macrocyclic encapsulation suppresses aggregation, resulting in dual-state emission in both solution and solid states. Core extension enables precise tuning of optoelectronic properties. Furthermore, tetrachlorinated Cycle-PBI-4Cl exhibits cyclization-promoted photoinduced intramolecular electron transfer, while the unilateral and bilateral sila-annulated Cycle-PBI-Si and Cycle-PBI-2Si demonstrate selective fluoride anion sensing through fluoride-induced Si–C bond cleavage. This work highlights the significant potential of this dual functionalization strategy, modifying both the short and long molecular axes of PBIs, for developing diverse functional materials.