Concepts and practices of
topological polymer chemistry have been described. First, systematic classification of nonlinear polymer topologies is introduced on the basis of topological considerations of constitutional isomerism in a series of alkanes (C
nH
2n+2), monocycloalkanes (C
nH
2n), and polycycloalkanes (C
nH
2n−2, C
nH
2n−4, etc.). Subsequently, topological isomerism occurring on randomly coiled, flexible polymer molecules having cyclic and linear structures is discussed. In practice, moreover, an “
electrostatic self-assembly and covalent fixation (ESA-CF)” process has been developed to construct complex multicyclic polymer topologies. The ESA-CF protocol has been extended in conjunction with effective linking/cleaving chemistry including a metathesis process and an alkyne-azide click reaction, to construct a variety of topologically significant multicyclic macromolecular topologies. By making use of such topological polymers, unprecedented opportunities have now been realized to provide new insights on fundamental polymer properties either in solution or bulk, in static or dynamic states, or in self-assemblies.
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