Effects of Axle‐Core, Macrocycle, and Side‐Station Structures on the Threading and Hydrolysis Processes of Imine‐Bridged Rotaxanes

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<jats:title>Abstract</jats:title><jats:p>Imine‐bridged rotaxanes are a new type of rotaxane in which the axle and macrocyclic ring are connected by imine bonds. We have previously reported that in imine‐bridged rotaxane <jats:bold>5</jats:bold>, the shuttling motion of the macrocycle could be controlled by changing the temperature. In this study, we investigated how the axle and macrocycle structures affect the construction of the imine‐bridged rotaxane as well as the dynamic equilibrium between imine‐bridged rotaxane <jats:bold>5</jats:bold> and [2]rotaxane <jats:bold>7</jats:bold> by using various combinations of axles (<jats:bold>1 A</jats:bold>,<jats:bold>B</jats:bold>), macrocycles (<jats:bold>2 a</jats:bold>–<jats:bold>e</jats:bold>), and side‐stations (XYL and TEG). In the threading process, the flexibility of the macrocycle and the substituent groups at the <jats:italic>para</jats:italic> position of the aniline moieties affect the preparation of the threaded imines. The size of the imine‐bridging station and the macrocyclic tether affects the hydrolysis of the imine bonds under acidic conditions.</jats:p>

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