Date

2009

Author

Yıldız, Ersin

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A monomer, 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl) benzenamine (SNS-NH2), was synthesized via the reaction of 1,4-di(2-thienyl)-1,4-butanedione with benzene-1,4-diamine. Chemical polymerization of the monomer yielded a polymer which was completely soluble in organic solvents. The chemical structures of both the monomer and the polymer were characterized by Nuclear Magnetic Resonance Spectroscopy (1H-NMR and 13C-NMR) and Fourier Transform Infrared (FTIR) Spectroscopy. The average molecular weight of the chemically synthesized polymer was determined by Gel Permeation Chromatography (GPC) as Mn = 2.2x103 g/mol. The electrochemical oxidative polymerization of SNS-NH2 was carried out via potentiodynamic electrolysis in the presence of LiClO4, NaClO4 (1:1) supporting electrolyte in acetonitrile. Electrochemical copolymerization of SNS-NH2 in the presence of 3,4-ethylenedioxythiophene (EDOT) was achieved in acetonitrile (ACN) / NaClO4/LiClO4 (0.1M) solvent-electrolyte couple via potentiodynamic electrolysis. Conductivities of samples were measured by four probe technique. Cyclic Voltammetry (CV) and UltravioletVisible Spectroscopy were used to investigate electrochemical behavior of the monomer and redox reactions of conducting polymers. Surface morphologies of the polymer films were investigated by Scanning Electron Microscope (SEM). Second part of the study was devoted to investigate the one of most interesting property of conducting polymers, the ability to switch reversibly between the two states of different optical properties, ‘electrochromism’. The electrochromic properties of the conducting polymers were investigated via spectroelectrochemistry, kinetic and colorimetry studies. Spectroelectrochemistry analysis of homopolymer, P(SNS-NH2), reflected electronic transitions at 376 and 650 nm indicating π-π* transition and polaron band formation respectively. The polymer has an electronic bandgap of 2.12 eV with a yellow color in the fully reduced form and a blue color in the fully oxidized form. Switching ability of the homopolymer was evaluated by kinetic studies upon measuring the % transmittance as 20.7 % at the maximum contrast point. The spectroelectrochemical behavior of the P(SNS-NH2-co-EDOT) compare to that of the homopolymer revealed solid evidence of copolymerization based upon the differences in the spectral signatures. Copolymer revealed multichromic property with five different colors at different applied potentials. Colorimetry studies for P(SNS-NH2-co-EDOT) proved that it is possible to provide fine tuning of these colors by varying applied potential during synthesis. The results of colorimetry, spectroelectrochemistry and FTIR studies showed the possible control of the color of the electrochromic material in a predictable, controlled and reproducible manner. As the last part of the study, dual-type complementary colored electrochromic devices (ECD) using P(SNS-NH2) and P(SNS-NH2-co-EDOT)/poly(3,4-ethylenedioxythiophene) (PEDOT) in sandwich configuration were constructed and evaluated. Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were investigated by UV-Vis Spectrophotometer and Cyclic Voltammetry. They have shown to possess good switching times, reasonable contrasts and high stabilities.

Subject Keywords

Chemistry., Electrochemical polymerization.

URI

http://etd.lib.metu.edu.tr/upload/2/12610291/index.pdf
https://hdl.handle.net/11511/18315

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Graduate School of Natural and Applied Sciences, Thesis