Utilizing the regioselectivity of perfluoropyridine towards the preparation of phenyoxyacetylene precursors for partially fluorinated polymers of diverse architecture

Regioselective nudeophilic substitution of perfluoropyridine with functionalized phenols provided a facile route toward the preparation of 2,6-bis(4-ethynylphenozy)-3,5-difluoro-4-phenoxypyridine, a monomer that can be polymerized neat via thermal [2 + 2 + 2] cyclopolymerizations affording intractable polyarylene networks or via copper-assisted step-growth 1,3-dipolar alkyne-azide click cycloaddition reactions with bis(azidomethyl) benzene. Both reactive pathways afforded polymers with high thermal stability and good char yields, which is comparable to acetylene-based resins. Notably, the opportunity for programmable thermal properties is realized through the operationally simple monomer synthesis was shown to be adaptive to various regioselective and nucleophile addition scenarios that can lead to the production of a library of perfluoropyridine monomers. Herein, we highlight the synthesis and characterization of these new perfluoropyridine-based polymer architectures for potentially tunable high performance applications.