Synthesis of Polymeric Topological Isomers through Electrostatic Self‐Assembly and Covalent Fixation with Star Telechelic Precursors

Summary: A pair of macromolecular constitutional isomers having topologically distinctive, dicyclic constructions, that is, θ‐shaped and manacle‐shaped polymers, has been synthesized from a polymer self‐assembly, comprised of three‐armed star poly(tetrahydrofuran) [poly(THF)] having N ‐phenylpyrrolidinium salt end groups carrying dicarboxylate counteranions ( 1S / 2d ). The presence of the two constitutional polymeric isomers was confirmed by means of a reversed‐phase liquid chromatography (RPC) technique. Moreover, size exclusion chromatography (SEC) showed that a major component possesses notably larger hydrodynamic volume than the others, and is assignable as a manacle‐shaped isomer while a minor component is assigned as a θ‐shaped isomer. The statistics of the covalent‐linking process of 1S / 2d were consistent with the other experimental results.An “electrostatic self‐assembly and covalent fixation” process of a trifunctional star‐shaped precursor gives rise to θ‐shaped and manacle‐shaped polymers.