Precision synthesis of linear oligorotaxanes and polyrotaxanes achieving well-defined positions and numbers of cyclic components on the axle.

Interest in macromolecules has increased because of their functional properties, which can be tuned using precise organic synthetic methods. For example, desired functions have been imparted by controlling the nanoscale structures of such macromolecules. In particular, compounds with interlocked structures, including rotaxanes, have attracted attention because of their unique supramolecular structures. In such supramolecular structures, the mobility and freedom of the macrocycles are restricted by an axle and dependent on those of other macrocycles, which imparts unique functions to these threaded structures. Recently, methods for the ultrafine engineering and synthesis, as well as functions, of "defined" rotaxane structures that are not statistically dispersed on the axle (i.e., control over the number and position of cyclic molecules) have been reported. Various synthetic strategies allow access to such well-defined linear oligo- and polyrotaxanes, including [1]rotaxanes and [n]rotaxanes (mostly n > 3). These state-of-the-art synthetic methods have resulted in unique functions of these oligo-and polyrotaxane materials. Herein, we review the effective synthetic protocols and functions of precisely constructed one-dimensional oligomers and polymers bearing defined threaded structures, and discuss the latest reports and trends.