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Abstract 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. 

Abstract Cyclophanes are a fundamentally interesting class of compounds that host a wide range of unique and emergent properties. However, synthesis of complex and/or functionalized cyclophanes can often suffer from harsh reaction conditions, long reaction times, and sometimes low yields using stepwise methods. We have previously reported an efficient, high‐yielding, metalloid‐directed self‐assembly method to prepare disulfide, thioether, and hydrocarbon cyclophanes and cages that feature mercaptomethyl‐arenes as starting materials. Herein, we report the synthesis of 21 new disulfide and thioether assemblies that expand this high yielding self‐assembly method to a wide breadth of macrocycles and cages with diverse structures. Remarkably, the high‐yielding, efficient syntheses still proceed under dynamic covalent control using electron‐deficient, heteroaryl, cycloalkyl, spiro, and even short alkenyl/alkynyl substrates.