Double-Bridging Increases the Stability of Zinc(II) Metal–Organic Cages

A key feature of coordination cages is the dynamic nature of their coordinative bonds, which facilitates the synthesis of complex polyhedral structures and their post-assembly modification. However, this dynamic nature can limit cage stability. Increasing cage robustness is important for real-world use cases. Here we introduce a double-bridging strategy to increase cage stability, where designed pairs of bifunctional subcomponents combine to generate rectangular tetratopic ligands within pseudo-cubic Zn₈L₆ cages. These cages withstand transmetalation, the addition of competing ligands, and nucleophilic imines, under conditions where their single-bridged congeners decompose. Our approach not only increases the stability and robustness of the cages while maintaining their polyhedral structure, but also enables the incorporation of additional functional units in proximity to the cavity. The double-bridging strategy also facilitates the synthesis of larger cages, which are inaccessible as single-bridged congeners.