Synthesis of polymeric topological isomers through electrostatic self‐assembly and covalent fixation with telechelic poly(THF) having cyclic ammonium salt groups

A pair of macromolecular constitutional isomers having topologically distinctive constructions, ie θ ‐shaped and manacle‐shaped polymers, has been synthesized through covalent conversion of an electrostatic polymer self‐assembly comprised of bifunctional linear poly(tetrahydrofuran) [poly(THF)] having N ‐phenylpyrrolidinium salt end groups carrying tricarboxylate counteranions ( 1 ) under various dilutions. The presence of the two constitutional polymeric isomers was revealed by means of a reverse‐phase liquid chromatography (RPLC) technique. Moreover, size‐exclusion chromatography (SEC) confirmed that one major component possesses notably larger hydrodynamic volume than another, and is assigned as a manacle‐shaped isomer while a minor component as a θ ‐shaped isomer. Further details of this unique process were investigated by RPLC analysis of topological isomer products obtained from a series of poly(THF) precursors, 1 , having different molecular weights. Copyright © 2003 Society of Chemical Industry