α-Cyclodextrin (CD)-based size-complementary [3]rotaxanes with alkylene axles were prepared in one-pot by end-capping reactions with aryl isocyanates in water. The selective formation of [3]rotaxane with a head-to-head regularity was indicated by the X-ray structural analyses. Thermal degradation of the [3]rotaxanes bearing appropriate end groups proceeded by stepwise dissociation to yield not only the original components but also [2]rotaxanes. From the kinetic profiles of the deslippage, it turned out that the maximum yield of [2]rotaxane was estimated to be 94 %. Thermodynamic studies and NOESY analyses of such rotaxanes revealed that [2]rotaxanes are specially stabilized, and that the dissociation capability of the [3]rotaxanes to the components can be adjusted by controlling the structure of the end groups, direction of the CD groups, and length of the alkylene axle.
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