Self-Assembly Route to Perylene Diimide(PDI)-Bridged Cyclophanes

This work reports the synthesis and self-assembly of perylene diimide (PDI)-containing macrocycles designed for facile and high-throughput production of shape-persistent, macrocyclic organic electronic materials. Specifically, utilizing dynamic covalent chemistry (DCvC), this work showcases ditopic thiols can be utilized as building blocks toward 3D materials with defined porosity, low-lying unoccupied molecular orbitals, and intrinsic fluorescence. The PDI disulfide-linked macrocycles are generated in a single step from the thiolic building block to yield dimeric through pentameric assemblies in overall 95% combined yield; moreover, following self-assembly, the disulfide ensemble is sulfur extruded to the more kinetically stable thioether in 79% combined yield. The modular design suggests these methods can be used to easily self-assemble other electronically active precursors for utility in porous macrocyclic materials where stepwise pathways may be laborious and/or low yielding. A pnictogen-assisted dynamic disulfide self-assembly method provides PDI-containing cyclophanes in a high-yielding, efficient, and scalable reaction. The macrocycles show enhanced properties over monomers and linear congeners and can serve as hosts for electron-rich guests. image