Regulating supramolecular interactions in dimeric macrocycles.

Supramolecular behavior is highly dependent on many factors, including complicated microenvironments and weak interactions. Herein, we describe tuning supramolecular architectures of rigid macrocycles by synergistic effects of their geometric configurations, sizes, and guests. Two paraphenylene-based macrocycles are anchored onto different positions in a triphenylene derivative, resulting in dimeric macrocycles with different shapes and configurations. Interestingly, these dimeric macrocycles show tunable supramolecular interactions with guests. In solid state, a 2 : 1 host-guest complex was observed between 1a and C 60 /C 70 , while an unusual 2 : 3 host-guest complex 3C 60 @(1b) 2 can be observed between 1b and C 60 . This work expands the scope of the synthesis of novel rigid bismacrocycles and provides a new strategy to construct different supramolecular systems.