Organic Cage Rotaxanes

Organic cages are a robust class of molecular hosts with a myriad of applications in materials science. Despite this, there has been a paucity of explorations into the modification of their properties via external functionalization. In this work, [n]rotaxanes featuring unoccupied organic cages as stopper components and a small 2,2′‐bipyridine macrocycle were constructed using the active metal template (AMT) approach. By exploiting a scrambling methodology, it was possible to synthesize cages with a defined number of interlocked components (n = 2–4). The gas uptake, solubility, and thermal properties of the interlocked systems were compared against those of their constituent, non‐interlocked components. In this manner, we were able to demonstrate the potential of exploiting the mechanical bond for modulating the physiochemical properties of these molecular materials.