Syntheses of conducting polymers of 3-ester substituted thiophenes and characterization of their electrochromic properties

Çamurlu, Pınar
In this study three different 3-ester substituted thiophene monomers were synthesized via esterification reaction of 3-thiophene ethanol with adipoyl chloride or sebacoyl chloride or octanoyl chloride in the presence of triethylamine at 00C. Characterizations of the monomers were performed by 1H-NMR, 13C-NMR, FTIR, DSC, TGA techniques. Electrochemical behavior of the monomers both in presence or absence of BFEE were studied by cyclic voltammetry. Results showed the astonishing effect of BFEE on the polymerization, where free standing films of the homopolymers could be synthesized. Copolymers of the monomers with thiophene or 3-methyl thiophene were synthesized at constant potential electrolysis and the resultant polymers were characterized by FTIR, DSC, TGA, SEM and conductivity measurements. 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’. 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 satisfactory electrochromic properties like short switching time and stability. Generally the homopolymers displayed color changes between yellow, green and blue colors upon variation of applied potentials. Fine tuning of the colors of the polymers were accomplished by techniques like copolymerization and lamination. These studies were supported with experiments like spectroelectrochemistry and FTIR. Results showed the possible control of the color of the electrochromic material in a predictable, controlled and reproducible manner. Yet, it was possible to achieve different tones of yellow, green, orange color in neutral state of these materials. As the last part of the study, dual type electrochromic devices based on polymers of 3-ester substituted thiophenes with poly(3,4-ethylenedioxythiophene) were constructed, where the former and the later functioned as anodically and cathodically coloring layers respectively. Spectroelectrochemistry, switching ability, stability, open circuit memory and color of the devices were investigated and the results revealed that these devices have satisfactory electrochromic parameters.


Electrochromic properties and electrochromic device application of copolymer of N-(4-(3-thienyl methylene)-oxycarbonylphenyl)maleimide with thiophene
Ak, Metin; Camurlu, Pinar; Yilmaz, Faruk; Cianga, Luminita; Yagci, Yusuf; Toppare, Levent Kamil (2006-12-05)
A new copolymer of N-(4-(3-thienyl methylene)-oxycarbonylphenyl)maleimide (MBThi) with thiophene [P(MBThi-co-Th)] was synthesized electrochemically in the presence of tetrabutylammonium tetrafluoroborate as the supporting electrolyte, in acetonitrile/borontrifluoride ethylether solvent mixture (80 : 20, v/v). Spectroelectrochemical analysis of the resulting copolymer reflected electronic transitions at 440, 730, and similar to 1000 nm, revealing pi-pi* transition, polaron, and bipolaron band formation, resp...
Synthesis and characterization of thiophen-3-yl-acetic acid 4-pyrrol-1-yl-phenyl ester and its conducting polymers
Bingöl, Bahar; Toppare, Levent Kamil; Department of Chemistry (2003)
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 ele...
Synthesis and characterization of a bifunctional amido-thiophene monomer and its copolymer with thiophene and electrochemical properties
AK, M; Çırpan, Ali; Yılmaz, Fatih; YAGCI, Y; Toppare, Levent Kamil (2005-05-01)
A bifunctional amido-thiophene namely hexamethylene (bis-3-thiophene acetamide) (HMTA) was synthesized by the reaction of 3-thiophene acetic acid with hexamethylene diamine. Copolymerization in the presence of thiophene was achieved electrochemically in tetrabutylammonium tetrafluoroborate/acetonitrile (TBAFB/AN). Spectroelectro-chemical analysis of the resulting copolymer [P(HMTA-co-Th)] reflected electronic transitions at 505 nm, 740 nm and similar to 1000 nm, revealing pi to pi* transition, polaron and b...
Multipurpose acetic acid functionalized carbazole derivatives: Synthesis, electrochemical properties and electrochromic device applications
Özdemir Hacıoğlu, Şerife; YİĞİT, DENİZ; Akbey, Tuba E.; UDUM, YASEMİN; GÜLLÜ, MUSTAFA; DEPCİ, TOLGA; Toppare, Levent Kamil (2022-03-01)
In this study, synthesis of two multifunctional acetic acid functionalized carbazole bearing monomers; 243,6-bis(2,3-dihydrothieno [3,4-b] [1,4]dioxin-5-yl)-9H-carbazol-9-yl)acetic acid (Ml) and 3,6-dithien-2-yl-9H car bazol-9-ylaceticacid (M2) via Stille cross-coupling reaction was reported. Obtained monomers were electro-chemically polymerized in 0.1 M TBAPF(6)/DCM/ACN (5:95, v:v) solution and characterized in terms of electrochemical, spectroelectrochemical and electrochromic switching behaviors. When po...
Syntheses of new monomeric and polymeric units and electrochemical behaviors for the use in electrochromic applications
Zaifoğlu, Nazlı Buket; Toppare, Levent Kamil; Çırpan, Ali; Department of Chemistry (2013)
4'-(Tert-butyl)-4,7-di(thiophen-2-yl)spiro[benzo[d]imidazole-2,1'-cyclohexane], 4,7-di([2,2'-bithiophen]-5-yl)-4'-(tert-butyl)spiro[benzo[d]imidazole-2,1'-cyclohexane], 4'-(tert-butyl)-4,7-bis(thieno[3,2-b]thiophen-2-yl)spiro[benzo[d]imidazole-2,1'- cyclohexane] were synthesized, electrochemically polymerized and electrochromic properties of resultant polymers were investigated. The monomers were characterized by nuclear magnetic resonance spectroscopy (1H-NMR, 13C-NMR). Cyclic voltammetry (CV) and ultravio...
Citation Formats
P. Çamurlu, “Syntheses of conducting polymers of 3-ester substituted thiophenes and characterization of their electrochromic properties,” Ph.D. - Doctoral Program, Middle East Technical University, 2006.