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.