Designing unusual polymer topologies by electrostatic self-assembly and covalent fixation

A novel protocol for designing a variety of topologically unique multicyclic polymer architectures, such as mono-, bi-, and tricyclic polymers as well as topological isomers; has been proposed on the basis of an electrostatic self-assembly of polymer precursors having five-membered cyclic ammonium salt groups accompanying plurifunctional carboxylate counteranions. Upon dilution in an organic medium at a concentration of below a gram per liter, the multiple aggregates of the polymer precursors completely dissociate into a smallest assembly, and cations and anions balance the charge. The subsequent covalent fixation through the ring-opening reaction of cyclic ammonium salt groups by carboxylate counteranions provides an efficient means for a variety of polymer architectures comprising mono- and multicyclic polymer units.