Synthesis, Structure, and Dynamic Properties of Hybrid Organic−Inorganic Rotaxanes

The synthesis and characterization of a series of hybrid organic−inorganic [2]rotaxanes is described. The ring components are heterometallic octa- ([Cr7MF8(O2CtBu)16]; M = Co, Ni, Fe, Mn, Cu, Zn, and Cd) nuclear cages in which the metal centers are bridged by fluoride and pivalate (tBuCO2−) anions; the thread components feature dialkylammonium units that template the formation of the heterometallic rings about the axle to form the interlocked structures in up to 92% yield in conventional macrocyclization or one-pot ‘stoppering-plus-macrocyclization’ strategies. The presence in the reaction mixture of additives (secondary or tertiary amines or quaternary ammonium salts), and the nature of the stoppering groups (3,5-tBu2C6H3CO2− or tBuCONH−), can have a significant effect on the rotaxane yield. The X-ray crystal structures of 11 different [2]rotaxanes, a pseudorotaxane, and a two-station molecular shuttle show two distinct types of intercomponent hydrogen bond motifs between the ammonium groups of the organic thread and the fluoride groups of the inorganic ring. The different hydrogen bonding motifs account for the very different rates of dynamics observed for the heterometallic ring on the thread (shuttling slow; rotation fast).