ABSTRACT SYNTHESIS AND CHARACTERIZATION OF THIOPHEN-3-YL ACETIC ACID 4-PYRROL-1-YL PHENYL ESTER AND ITS CONDUCTING POLYMERS Bing&ouml / l, Bahar M.Sc., Department of Chemistry Supervisor: Prof. Dr. Levent Toppare November 2003, 54 pages Thiophen-3-yl acetic acid 4-pyrrol-1-yl phenyl ester (TAPE) monomer was synthesized by the reaction of thiophene acetic acid with thionyl chloride, and further reaction of thiophen-3-yl-acetyl chloride with 4-pyrrol-1-yl phenol. Electrochemical behavior of this monomer (TAPE) was determined by cyclic voltammetry. Homopolymers were achieved both by using electrochemical and chemical polymerization techniques. Copolymers of TAPE in the presence of bithiophene and pyrrole were synthesized by potentiostatic electrochemical polymerization in acetonitrile-tetrabutylammonium tetrafluoroborate (TBAFB) solvent-electrolyte couple. The chemical structures were confirmed both by Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Differential Scanning Calorimetry (DSC) and Thermal Gravimetry Analysis (TGA) were used to examine the thermal behavior of synthesized conducting homopolymers and copolymers. The morphologies of the films were investigated by Scanning Electron Microscope (SEM). Two-probe technique was used to measure the conductivities of the samples. Moreover, investigations of electrochromic and spectroelectrochemical properties of poly(TAPE) and TAPE/BiTh copolymer were done. Keywords: Conducting copolymers, electrochromic properties

Different substituted thiophene and pyrrole monomers namely hexamethylene (bis-3-thiopheneacetamide) (HMTA), N-(4-(3-thienylmethylene)-oxycarbonylphenyl)maleimide (MBThi), 2,4,6-Tris-(4-pyrrol-1-yl-phenoxy)-[1,3,5]triazine (TriaPy), 2,4,6-Tris-(thiophen-3-ylmethoxy)-[1,3,5] triazine (TriaTh), and N-(2-(thiophen-3-yl)methylcarbonyloxyethyl) maleimide (NMT) were synthesized. The chemical structures of the monomers were characterized by Nuclear Magnetic Resonance (1H-NMR and 13C-NMR) and Fourier Transform Infrared (FTIR) Spectroscopies. Electrochemical behavior of the monomers in the presence and absence of comonomers were studied by cyclic voltammetry. Subsequently, monomers were homopolymerized and copolymerized via electrochemical methods and the resultant polymers were characterized by FTIR, Scanning Electron Microscopy (SEM) and conductivity measurements. Second part of the study was devoted to investigate one of most interesting property of conducting polymers, the ability to switch reversibly between the two states of different optical properties, &ldquo / electrochromism&rdquo / . In recent years there has been a growing interest in application of conducting polymers in electrochromic devices. Thus, electrochromic properties of the synthesized conducting polymers were investigated by several methods like spectroelectrochemistry, kinetic and colorimetry studies. Spectroelectrochemistry experiments were performed in order to investigate key properties of conjugated polymers such as band gap, maximum absorption wavelength, the intergap states that appear upon doping and evolution of polaron and bipolaron bands. Switching time and optical contrast of the homopolymers and copolymers were evaluated via kinetic studies. Results implied the possible use of these materials in electrochromic devices due to their good electrochromic properties.

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 Ultraviolet&ndash / Visible 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, &lsquo / electrochromism&rsquo / . 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 &amp / #960 / -&amp / #960 / * 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.

Synthesis of 2-[(3-thienylcarbonyl)oxy]ethyl 3-thiophene carboxylate (TOET), 2,3-bis-[(3-thienylcarbonyl)oxy]propyl 3-thiophene carboxylate (TOPT), and 3-[(3-thienylcarbonyl)oxy]-2,2-bis{[(3-thienylcarbonyl)oxy]}propyl 3- thiophene carboxylate (TOTPT), and their copolymerization either with thiophene or pyrrole were achieved. The chemical structures of the monomers were investigated by Nuclear Magnetic Resonance Spectroscopy (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Electrochemical behavior of the monomers and copolymers were studied by cyclic voltammetry (CV). The resultant conducting copolymers were characterized via FTIR, Thermal Gravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC), and morphologies of the films were inspected by Scanning Electron Microscope (SEM). Conductivities of the samples were measured by using four-probe technique. The electrochromic and spectroelectrochemical properties of the copolymers were investigated.

Synthesis and characterization of conducting copolymers were achieved by using thiophene-3-yl acetic acid cholesteryl ester (CM) and poly (3-methylthienyl methacrylate) (PMTM). A new polythiophene containing a cholesteryl side chain in the &amp / #946 / -position was chemically polymerized in nitromethane/carbon tetrachloride using FeCl3 as the oxidizing agent. Polymerization was also achieved by constant current electrolysis in dichloromethane. Subsequently, conducting copolymers of thiophene-3-yl acetic acid cholesteryl ester (CM), PCM1 (obtained from chemical polymerization method), PCM4 (obtained from constant current electrolysis) with pyrrole were synthesized. Thiophene functionalized methacrylate monomer (MTM) was synthesized via esterification of the 3-thiophene methanol with methacryloyl chloride. The methacrylate monomer was polymerized by free radical polymerization in the presence of azobis (isobutyronitrile) (AIBN) as the initiator. Graft copolymers of poly (3-methylthienyl methacrylate)/polypyrrole, (PMTM2/PPy) and poly (3-methylthienyl methacrylate)/polythiophene, (PMTM2/PTh) were synthesized by constant potential electrolyses. PMTM2 coated Pt electrodes were utilized as the anode in the polymerization of pyrrole and thiophene. Moreover, oxidative polymerization of PMTM1 was studied by galvanostatic and chemical techniques. Characterizations of the samples were performed by CV, FTIR, NMR, DSC, TGA and SEM analyses. Electrical conductivities were measured by the four-probe technique. Immobilization of invertase in conducting copolymer matrices, poly (3-methylthienyl methacrylate) with pyrrole and thiophene was achieved by constant potential electrolysis using the sodium dodecyl sulfate as the supporting electrolyte. Polythiophene was also used for immobilization matrices. Cholesterol oxidase has been immobilized in conducting copolymer of thiophene-3-yl acetic acid cholesteryl ester with polypyrrole (CM/PPy) and polypyrrole (PPy) by the electropolymerization method. p-Toluene sulfonic acid was used as a supporting electrolyte. Kinetic parameters (Kinetic parameters / Vmax and Michaelis-Menten constant / Km) and operational stability of enzyme electrodes were investigated. Surface morphology of the films was also examined.

Synthesis and characterization of thiophene ended poly-&amp / #949 / -caprolactone (PCL) and oxalic acid dithiophen-3-yl methyl ester (ODME) and their copolymers with both pyrrole and thiophene were achieved. Chemical structure of the precursor polymer and monomer were investigated Redox behavior of polymer and monomers were determined by Cyclic Voltammetry (CV). Structural characterization of samples were carried out by 1H, 13C Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Conductivities of the films were measured by using four probe technique. Thermal analyses of conducting copolymers were investigated via Differential Scanning Calorimetry (DSC) and Thermal Gravimetry Analysis (TGA). The morphologies of the copolymer films were examined by Scanning Electron Microscopy (SEM). Electrochromic and spectroelectrochemical behavior of the copolymers were investigated, and their ability of employment in device construction has been examined.

Immobilization of tyrosinase in conducting copolymer matrices of pyrrole functionalized polydimethylsiloxane/polypyrrole (PDMS/PPy) were achieved by electrochemical polymerization. The polysiloxane/polypyrrole/tyrosinase electrode was constructed by the entrapment of enzyme in conducting matrices during electrochemical copolymerization. Maximum reaction rate (Vmax) and Michaelis-Menten constant (Km) were investigated for immobilized enzyme. Enzyme electrodes were prepared in two different electrolyte/solvent systems. The effect of supporting electrolytes, p-toluene sulfonic acid and sodium dodecyl sulfate on the enzyme activity and film morphology were determined. Temperature and pH optimization, operational stability and shelf-life of enzyme electrodes were also examined. Phenolic contents of green and black tea were determined by using enzyme electrodes.

Two new monomers / 2-benzyl-5,12-dihydro-2Hpyrrolo[ 3&rsquo / ,4&rsquo / :2,3][1,4]dioxocino[6,7-b]quinoxaline (DPOQ) and 5,12- dihydrothieno[3&rsquo / ,4&rsquo / :2,3][1,4]dithiocino[6,7-b]quinoxaline (DTTQ), were synthesized. The chemical structures of the monomers were characterized by Nuclear Magnetic Resonance (1H-NMR), Fourier Transform Infrared (FTIR) and Mass Spectrometry (MS). Copolymer of DPOQ with bithiophene (BT) was synthesized via potentiostatic electrochemical polymerization in acetonitrile (ACN)-tetrabutylammonium tetrafluoroborate (TBAFB) solvent-electrolyte couple. For DTTQ, copolymerization with bithiophene was achieved via potentiodynamic method in dichloromethane (DCM)-tetrabutylammonium hexafluorophosphate (TBAFP) solvent-electrolyte couple. Characterizations of the resulting copolymers were performed by cyclic voltammetry (CV), FTIR, Scanning Electron Microscopy (SEM) and UV-Vis Spectroscopy. Four-probe technique was used to measure the conductivities of the samples. Moreover, the spectroelectrochemical and electrochromic properties of the copolymer films were investigated. In addition, dual type polymer electrochromic devices (ECDs) based on P(DPOQ-co-BT) and P(DTTQ-co-BT) with poly(3,4- ethylenedioxythiophene) (PEDOT) were constructed. Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were studied. They were found to have good switching times, reasonable contrasts and optical memories.