Cucurbit[8]uril Mediated Supramolecular Heterodimerisation and Photoinduced [2+2] Heterocycloaddition to Generate Unexpected [2]Rotaxanes

In contrast to the self‐assembly of homosupramolecules, the self‐assembly of heterosupramolecules is more challenging and significant in various fields. Herein, we design and investigate a cucurbit[8]uril‐mediated heterodimerisation based on an arene‐fluoroarene strategy. Furthermore, the heteroternary complex is found to be able to undergo a photoinduced [2+2] heterocycloaddition, resulting in the formation of an unexpected [2]rotaxane. This work demonstrates a novel supramolecular heterodimerisation system that not only contributes to the development of photoisomerisation systems, but also enriches synthetic methods for mechanically interlocked molecules.