Poly(cyclopentadienylene ethynylene)s: Breaking Conventional Polyenyne Motifs

Conjugated polyenynes comprising dienyne constituents have been synthesized for the first time, expanding the architectural scope of this unique polymer class. The poly(cyclopentadienylene ethynylene)s (PCE)s are soluble in common organic solvents, a rare feature among polyenynes, and possess physicochemical properties that are influenced by the structure of their solubilizing groups. A comparative analysis between the PCEs and other soluble polyenynes, poly(arylene ethynylene)s, and a hybrid of both polymer classes show among other characteristics that the inclusion of cyclopentadienes into the conjugated backbone significantly reduces electronic transition energies while completely suppressing photoluminescence.