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Transition-metal-free synthesis of poly(phenylene ethynylene)s with alternating aryl-perfluoroaryl units.

A catalytic amount of fluoride salt is all that is required to generate high molecular weight poly(phenylene ethynylene)s from silylacetylene-functionalized monomers and C6F6. The sole side product is gaseous fluorotrimethylsilane and the catalyst is removed simply by washing with water. The polymerization proceeds through a reactive intermediate, causing significant deviation from theory describing the relationship between comonomer stoichiometry and degree of polymerization for classical step-growth polymerizations.