Synthesis and Characterization of Poly(p-phenylene ethynylene)s with nitroxyl radical endgroups

Abstract

The generation of terminal N-Hydroxyl substituents in p-phenylene ethynylene based compounds is presented. P-phenylene ethynylene derivatives were synthesized in a Sonogashira coupling reaction. N-Hydroxyl groups could be introduced by lithiation of iodine moieties and subsequent reaction with the 2-methyl-2-nitrosopropane generated by the cleavage of its dimer. The synthesis by lithiation was found to be more effective compared to the reaction with the Grignard reagent and the chloro-derivative. The resulting compounds were characterized by 1H NMR, UV and PL spectroscopy and were shown to be sensitive towards oxidation. This new approach of introducing additional charge carriers by nitroxyl endgroups might enable conjugated polymers with enhanced conductivity.