Topochemical 1,3-dipolar cycloaddition polymerization assisted by non-covalent interactions

Abstract

An efficient topochemical azide–alkyne cycloaddition polymerization of monomers, which comprised phenylene and tetrafluorophenylene units linked by alkylene linkers and terminated by azide and alkyne groups, was achieved through a supramolecular approach. The introduction of amide moieties provided hydrogen bonding to strengthen molecular preorganization in the crystal lattice. Through the cooperative intermolecular arene–perfluoroarene interactions and hydrogen bonding, alternating packing of reactive groups between molecules was obtained with the prearrangement of azide and alkyne functional groups in the crystalline state. The prearrangement facilitated the reaction and resulted in a more than 90% regioselectivity to 1,4-triazole products. This research provides a direct way for efficient and green polymerizations with regioselectivity and the regioselectivity can be modulated by the molecular structure.