Abstract
(Co)Polymers containing pentafluorophenylacetylene (F5PA) have been prepared for the first time mediated by [Rh(nbd)Cl]2/NEt3 to give materials with properties typical of poly(phenylacetylene)s prepared with this catalyst/co-catalyst combination. We demonstrate that the F5PA repeat units in these new (co)polymers serve as convenient reactive species for postpolymerization modification with thiols via para-fluoro aromatic nucleophilic substitution reactions to give an entirely new family of novel thioether-functional polyene materials accompanied by absorption maxima shifts of up to 130 nm. Finally, we briefly examine the electrochemical properties of these new fluorinated polyene materials and highlight the distinct difference in behaviour of the F5PA homopolymer versus polyphenylacetylene, copolymers and functional derivatives.