Thermally Driven Dynamics of a Rotaxane Wheel about an Imidazolium Axle inside a Metal-Organic Framework

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 Zn^II 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), ² H 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.