Designed Synthesis of an Aluminum Molecular Ring Based Rotaxane and Polyrotaxane

Mechanically interlocked molecules, such as rotaxanes, have drawn significant attention within supramolecular chemistry. Although a variety of macrocycles have been thoroughly explored in rotaxane synthesis, metal‐organic macrocycles remain relatively under‐investigated. Aluminum molecular rings, with their inner cavities and numerous binding sites, present a promising option for constructing rotaxanes. Here, we introduce an innovative “ring‐donor⋅⋅⋅axle‐acceptor” motif utilizing Al8 molecular rings, enabling the stepwise assembly of molecules, complexes, and polymers through tailored coordination chemistry. This novel approach can not only be applied to macrocycle‐based systems like catenanes but also enhance specific functionalities progressively. The multisite and adaptive Al8 macrocycle demonstrates a groundbreaking capacity to sequentially encapsulate molecules, complexes, and polymers through “ring‐donor⋅⋅⋅axle‐acceptor” interactions. This progressive encapsulation culminates in the formation of an endless polyrotaxane structure, “the Al8 rock sugar gourd”. These distinct host–guest interactions bestow the Al8 macrocycles with customizable optical‐limiting functionalities.