1,2-Dicyanotetrafluorobenzene (1,2-DCTB) was polycondensed with various flexible diphenols in a molar ratio of 1:2, and experimental parameters such as the concentration and temperature were varied. Certain diphenols allowed a complete substitution of all C-F bonds, so perfect multicyclic polyethers (BnCN, where B stands for bridge units, C represents cycles, and N is the degree of polymerization) were the main reaction products. Despite complete conversion, gelation was avoidable under optimized reaction conditions. However, in the case of 1,3-dicyanotetrafluorobenzene (1,3-DCTB), complete tetrasubstitution was not feasible with a feed ratio of 1:2. Yet, because of the inductive and mesomeric electronic interactions of all substituents in 1,3-DCTB, the three C-F groups in the ortho position with respect to the cyano groups were significantly more reactive than the fourth C-F bond. Therefore, polycondensations with diphenols in a 3:2 feed ratio showed a relatively clean course, yielding soluble multi-cycles of structure Bn/2CN. All the multicyclic polyethers were amorphous and possessed molar mass distributions with polydispersities greater than 2. Heating with Cu2+ salts caused crosslinking of the multicycles derived from 1,2-DCTB because of the formation of phthalocyanine complexes. (c) 2006 Wiley Periodicals, Inc.