Catenanes of Twin-Cavity Cages

Catenanes, interlocked molecular architectures, hold promise for molecular machines and catalysis, yet constructing complex topologies from multicavity cages remains challenging. Herein, we report the selective synthesis of an interwoven dimeric catenane comprising twin-cavity organic cages, achieved through a one-pot reaction between a trialdehyde planar panel and a triamine linker. This efficient synthesis is rationally guided by our probabilistic model. The model begins with a topological analysis that captures the essential spatial arrangement of the planar panels, which provides the main driving force for catenane formation and defines the interwoven and chain-like topological isomers. A probability density function that accounts for the π-π stacking interactions between the planar panels is then incorporated into the probabilistic model, enabling the semiquantitative prediction that the interwoven isomer is predominantly favored over the chain-like counterpart. Single-crystal X-ray diffraction unambiguously confirms the interwoven structure, revealing the stabilizing π-π stacking between the panels. This integrated theoretical-experimental approach offers a rational strategy for the selective one-pot synthesis of sophisticated interlocked architectures among various isomers.