A rigid H-shaped, [2]rotaxane molecular shuttle comprised of an axle containing two benzimidazole recognition sites and a central 2,2'-bipyridyl (bipy) group interlocked with a 24-crown-8 (24C8) wheel was synthesized using a threading followed by stoppering protocol. The central bipy chelating unit was shown to act as a speed bump that raised the barrier to shuttling for the [2]rotaxane. Coordination of a PtCl2 moiety to the bipy unit in a square planar geometry created an insurmountable steric barrier to shuttling. Addition of one equivalent of NaB(3,5-(CF3)2C6H3)4 removed one of the chloride ligands allowing for translation of the crown ether along the axle into the coordination sphere of the Pt(ii) centre but full shuttling of the crown ether could not be activated. In contrast, addition of Zn(ii) ions in a coordinating solvent (DMF) allowed shuttling to occur using a ligand exchange mechanism. DFT calculations showed this likely occurs via coordination of the 24C8 macrocycle to the Zn(ii) centre bound to the bipy chelate. This interplay of the rotaxane axle and wheel components is an example of a translationally active ligand that utilises the large amplitude displacement of a macrocycle along an axle in a molecular shuttle to access ligand coordination modes not possible with conventional ligand designs.
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