Electrochemical and spectroelectrochemical studies of poly(2,5-di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylthienyl) derivatives bearing azobenzene, coumarine and fluorescein dyes: Effect of chromophore groups on electrochromic properties

Yigit, Deniz
Udum, Yasemin Arslan
GÜLLÜ, Mustafa
Toppare, Levent Kamil
Three novel thiophene based monomers, 2,5-di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylthienyl derivatives, 1-{4-[(2,5-Di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl-3-thienyl) methoxy] phenyl}-2-phenyldiazene) (ETEAz), 4-[(2,5-Di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl-3-thienyl) methoxy]2H- chromen-2-one) (ETECo) and methyl 2-{6-[(2,5-Di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl-3-thienyl) methoxy]-3-oxo-3H-xanthen -9-yl} benzoate (ETEFlo), were synthesized and their conducting polymers were electrochemically prepared on ITO glass electrodes for the first time. The electroactive monomers were functionalized with strong chromophore groups such as azobenzene, coumarine and fluorescein in order to investigate the effect of chromophore units on electrochemical and spectroelectrochemical characteristics of corresponding conducting polymers. Spectroelectrochemical studies demonstrated that combination of a strong chromophore group with polymer backbone leads to significant changes in electronic and optoelectronic behaviors of resulting conducting polymers. PETEAz, PETECo and PETEFlo exhibited multicolored electrochromism with three distinct states. PETEAz revealed 33% (565 nm) and 52% (1270 nm) transmittance changes (Delta T%), while PETECo exhibited 40% (535 nm) and 64% (1245 nm) at their dominant wavelenghts. The optical contrasts of PETEFlo were measured as 15% (495 nm), 28% (560 nm) and 43% (1345 nm), which were lower than those of PETEAz and PETEFlo. It was observed that all conducting polymer films could be very quickly switched between their neutral and oxidized states in both visible and NIR regions. Switching times values were found to be 0.3 s at 565 nm and 0.4 s at 1270 nm for PETEAz, 0.4 s at 535 nm and 0.5 s at 1245 nm for PETECo, 0.4 s at 495 nm, 0.4 s at 560 nm and 0.7 s at 1345 nm. Moreover, the optical band gap values for PETEAz, PETECo and PETEFIo were calculated as 1.6 eV, 1.4 eV and 1.55 eV, respectively, from the onset of pi-pi* transition in polymer films' neutral states. a 2014 Elsevier Ltd. All rights reserved.


Electrochemical polymerization of 1-(4-nitrophenyl)-2,5-di(2-thienyl)-1 H-pyrrole as a novel immobilization platform for microbial sensing
Tuncagil, Sevinc; ODACI DEMİRKOL, DİLEK; Varis, Serhat; TİMUR, SUNA; Toppare, Levent Kamil (2009-09-01)
Two types of bacterial biosensor were constructed by immobilization of Gluconobacter oxydans and Pseudomonas fluorescens cells on graphite electrodes modified with the conducting polymer; poly(1-(4-nitrophenyl)-2,5-di(2-thienyl)-1 H-pyrrole) [SNS(NO2)]. The measurement was based on the respiratory activity of cells estimated by the oxygen consumption at -0.7 V due to the metabolic activity in the presence of substrate. As well as analytical characterization, the linear detection ranges, effects of electropo...
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...
Electrochemical and optical properties of novel terthienyl based azobenzene, coumarine and fluorescein containing polymers: Multicolored electrochromic polymers
Yigit, Deniz; Udum, Yasemin Arslan; GÜLLÜ, Mustafa; Toppare, Levent Kamil (Elsevier BV, 2014-01-01)
Three electroactive terthienyl based monomers, namely 1-phenyl-2-[4-(2,2':5',2 ''-terthien-3'-ylmethoxy)phenyl]diazene (TTAz), 4-(2,2':5',2 ''-terthien-3'-ylmethoxy)-2H-chromen-2-one (TTCo) and methyl 2-[3-oxo-6-(2,2':5',2 ''-terthien-3'-ylmethoxy)-3H-xanthen-9-yl] benzoate (TTFlo), were synthesized with good yields and their conducting polymers were electrochemically prepared on ITO electrode surfaces. The effect of chromophore type on electrochemical and optical properties of the polymers was investigated...
Synthesis and electrochromic properties of conducting polymers of 5,8-di(pyrrol-2-yl)-2,3-di(thiophen-2-yl) quinoxaline and its copolymers
Taşkın, Aslı Tuba; Toppare, Levent Kamil; Department of Chemistry (2009)
A novel electroactive monomer 5,8-Di(1H-pyrrol-2-yl)-2, 3-di(thiophen-2-yl) quinoxaline (PTQ) was successfully synthesized via Stille Coupling reaction between quinoxaline and pyrrole. Nuclear magnetic resonance (1H NMR and 13C NMR) and Mass spectroscopy were used to characterize the monomer. The monomer was electrochemically polymerized in the presence of tetrabutylammonium perchlorate (TBAP) as supporting electrolyte in dichloromethane. Monomer reveals relatively low oxidation potential at +0.70V. Spectro...
Electrochemical copolymerization of 2-substituted thiophene derivative linked by polyether bridge with thiophene
Cihaner, A; Önal, Ahmet Muhtar (2005-09-01)
New conducting copolymers have been synthesized via electrochemical oxidation of thiophene (Th) in the presence of monomer bis(2-thienyl)ethyl (1). Cyclic voltammetry (CV) studies showed that the presence of monomer I in the electrolytic solution greatly changes the CV behaviour of the formation of the polythiophene films. It is found that the increasing ratio of I was found to decrease electroactivity of copoly(I-Th). Electrochemical synthesis of copolymer films was achieved via constant potential electrol...
Citation Formats
D. Yigit, Y. A. Udum, M. GÜLLÜ, and L. K. Toppare, “Electrochemical and spectroelectrochemical studies of poly(2,5-di-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-ylthienyl) derivatives bearing azobenzene, coumarine and fluorescein dyes: Effect of chromophore groups on electrochromic properties,” ELECTROCHIMICA ACTA, pp. 669–677, 2014, Accessed: 00, 2020. [Online]. Available: https://hdl.handle.net/11511/46075.