ABSTRACT
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.
ABSTRACT
A new mechanically interlocked molecular linker was prepared by using ring-closing metathesis (Grubbsâ 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), 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.
ABSTRACT
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.
