The first green and fast photoinduced step-growth polymerization of 3,4- ethylenedioxythiophene (EDOT) producing high molecular weight poly (3,4- ethylendioxythiophene) (PEDOT) is reported. Phenacyl bromide was used as a single-component photoinitiating system under a broad wavelength range. The reported photooxidative polymerization technique has several advantages over the conventional oxidation methods (chemical/electrochemical) such as the use of green solvent and ambient conditions (room temperature and air atmosphere), doping of the polymer with bromide ions during the photopolymerization reaction, possibility to perform bulk photopolymerization and tune the irradiation wavelength depending on the phenacyl bromide concentration. Doped PEDOT synthesized under near-UV irradiation was thoroughly investigated using different spectral and chromatographic methods. It has high conductivity (1.6 S/cm), high molecular weight (32.5 kg/mol) and strong white light photoluminescence.
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