Allosteric release of cucurbit[6]uril from a rotaxane using a molecular signal

Rotaxanes can be regarded as storage systems for their wheel components, which broadens their application potential as a complement to the supramolecular systems that retain a mechanically interlocked structure. However, utilising rotaxanes in this way requires a method to release the wheel while preserving the integrity of all molecular constituents. Herein, we present simple rotaxanes based on cucurbit[6]uril (CB6), with an axis equipped with an additional binding motif that enables the binding of another macrocycle, cucurbit[7]uril (CB7). We demonstrate that the driving force behind the wheel dethreading originates from the binding of the signalling macrocycle to the allosteric site, leading to an increase in the system's strain. Consequently, the CB6 wheel leaves the rotaxane station overcoming the mechanical barrier. Portal-portal repulsive interactions between the two cucurbituril units play a crucial role in this process. Thus, the repulsive strength and the related rate of slipping off can be finely tuned by the length of the allosteric binding motif. Finally, we show that the CB6 wheel can be utilised within complexes with other guests in the mixture once released from the rotaxane.