A novel protocol for designing a variety of topologically unique multicycli
c 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 s
alt groups accompanying plurifunctional carboxylate counteranions. Upon dil
ution in an organic medium at a concentration of below a gram per liter, th
e multiple aggregates of the polymer precursors completely dissociate into
a smallest assembly, and cations and anions balance the charge. The subsequ
ent 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 u
nits.