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Synthesis, characterization and electrochromic properties of copolymer of 3-{[4-(thien-3-yl-methoxy)phenoxy]methyl}thiophene with thiophene
Authors:Ayça Erden  Mustafa Güllü
Institution:a Middle East Technical University, Department of Chemistry, 06531 Ankara, Turkey
b Dicle University, Department of Chemistry, 21280 Diyarbakir, Turkey
c Ankara University, Department of Chemistry, 06100 Ankara, Turkey
Abstract:(3-{4-(Thien-3-yl-methoxy)phenoxy]methyl}thiophene) (TMPMT) was synthesized via the reaction of 3-bromomethylthiophene with hydroquinone and characterized by nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). Electrochemical copolymerization of TMPMT with thiophene in acetonitrile/boron trifluoride diethyl etherate (AN/BFEE) solvent mixture was achieved using tetrabutylammonium tetrafluoroborate (TBAFB) as the supporting electrolyte. Resulting copolymer was characterized via cyclic voltammetry (CV), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), four probe technique conductivity measurement and UV-Vis spectroscopy. Spectroelectrochemical analysis of the copolymer P(TTMT-co-Th)] revealed that π-π electronic transition occurs at 427 nm with a band gap value of 2.20 eV. Copolymer gives brown color at the fully reduced state whereas; at fully oxidized state the film has a gray-blue color. Kinetic studies were carried out at the maximum contrast wavelength upon measuring the percent transmittance, T% (7.6%) and switching time (2.0 s) to examine the switching ability of the copolymer. Dual type electrochromic device (ECD) of P(TMPMT-co-Th) and poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed. Spectroelectrochemistry, switching ability, open circuit memory and stability of the device were examined by UV-Vis spectroscopy and cyclic voltammetry. The device switches between brown and blue at switching voltages of 0.0 V and 2.8 V with a short switching time of 1.4 s.
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