A new mechanically interlocked molecular linker was prepared by using ring‐closing metathesis (Grubbs I) to clip a [24]crown‐6 ether wheel around an axle containing both Y‐shaped diphenylimidazole and isophthalic acid groups. A metal–organic framework (MOF) material was prepared using this linker and ZnII ions. Single‐crystal X‐ray diffraction experiments showed that the MOF contains an imidazolium‐based rotaxane linked by dimeric [Zn2(NO3)(DEF)] secondary building units (SBUs). Variable‐temperature (VT), 2H solid‐state NMR spectroscopy was used to characterize the motion of the “soft” wheel component around the rigid “hard” lattice of the framework. At higher temperatures (above 150 °C), it was demonstrated that the 24‐membered, macrocyclic ring of the MOF undergoes rapid, thermally driven rotation about the axle inside the voids of the lattice.

A new templating motif for the formation of [2]pseudorotaxanes is described in which rigid, Y-shaped axles with an imidazolium core and aromatic substituents at the 2-, 4- and 5-positions interact with [24]crown-8 ether wheels ([24]crown-8 and dibenzo[24]crown-8). The Y-shape of the axle significantly enhances the association between axle and wheel when compared to simple imidazolium cations.

Two different recognition sites, one a T-shaped 2,4,7-triphenylbenzimidazolium and the other a Y-shaped 2,4,5-triphenylimidazolium are combined to construct a rigid bistable [2]rotaxane molecular shuttle on which the position of a 24-membered crown ether macrocycle can be controlled by acid-base chemistry. Molecular shuttling in both the neutral and dicationic versions were studied.