Synthesis of New Thienylene Pyrrole Monomers and Their Electropolymerizations

Eken, Serap
Carbas, Buket Bezgin
Akdağ, Akın
Önal, Ahmet Muhtar
In this study, four new 2,5-dithienylpyrroles (SNS) 1-(3-fluoro-phenyl)-2,5-di(thiophen-2-yl)-1H-pyrrole (m-FPTP), 1-(3-chlorophenyl)-2,5-di(thiophen-2-yl)-1H-pyrrole (m-ClPTP), 1-(3-bromo-phenyl)-2,5-di(thiophen-2-yl)-1H-pyrrole (m-BrPTP) and 1-(4-bromo-phenyl)-2,5-di(thiophen-2-yl)-1H-pyrrole (p-BrPTP) containing meta and para substituted benzene ring at the nitrogen atom were synthesized via Paal-Knorr condensation of 1,4-di(2-thienyl)-1,4-butanedione with corresponding halo-substituted anilines. The monomers were polymerized via potential cycling in LiClO4-acetonitrile (ACN) electrolytic solution. The replacement effect of halogen atoms as a substituent from para-to meta-positions and different halogen units (F, Cl, Br) at only meta-/para-positions in the structure on the electrochemical and optical properties of synthesized monomers/polymers were investigated. Computational investigations (M06/TZVP) were also performed on the monomer structures to support the electrochemical behavior of the monomers and to get more insight about the conformation of the structures. Furthermore, the synthesized polymer films exhibited reversible redox behavior accompanied with a reversible electrochromic behavior. It was also observed that the optical contrast value (Delta T%) for polymers was significantly improved when compared with their analogs in the literature. (C) The Author(s) 2014. Published by ECS. All rights reserved.


Investigation of Fluorine Atom Effect on Benzothiadiazole Acceptor Unit in Donor Acceptor Donor Systems
Çakal, Deniz; Akdağ, Akın; Önal, Ahmet Muhtar (The Electrochemical Society, 2019-07-12)
Synthesis of two new pi-conjugated monomers containing fluorine substituted benzothiadiazoles as acceptor units and 3,4-ethylenedioxythiophene (EDOT) as donor unit was accomplished by facilitating Stille cross-coupling reactions (4,7-bis(2,3-dihydrothieno[3,4-b][1,4] dioxin-5-yl)-5-fluorobenzo[c][1,2,5] thiadiazole (E2BTD-F) and 4,7-bis(2,3-dihydrothieno [3,4-b][1,4] dioxin-5-yl)-5,6-difluorobenzo[c][1,2,5] thiadiazole (E2BTD-2F)). NMR and HRMS spectra of newly synthesized compounds are in agreement with th...
Synthesis and characterization of a new soluble conducting polymer and its electrochromic devices
Sahin, Elif; Sahmetlioglu, Ertugrul; Akhmedov, Idris M.; Tanyeli, Cihangir; Toppare, Levent Kamil (Elsevier BV, 2006-10-01)
A new polythiophene derivative was synthesized by both chemical and electrochemical oxidative polymerization of 1-(perfluorophenyl)-2,5-di(2-thienyl)-1H-pyrrole (FPTPy). The structures of both the monomer and the soluble polymer were elucidated by nuclear magnetic resonance (H-1-NMR) and fourier transform infrared (FTIR). Polymer of FPTPy was also synthesized via potentiostatic electrochemical polymerization in acetonitrile (AN)/NaClO4/LiClO4 (0.1 M:0.1 M) Solvent-electrolyte couple. Characterizations of th...
Syntheses and Electrochemical Characterization of Low Oxidation Potential Nitrogen Analogs of Pedot as Electrochromic Materials
Hacioglu, Serife O.; Yigit, Deniz; Ermis, Emel; Soylemez, Saniye; GÜLLÜ, Mustafa; Toppare, Levent Kamil (The Electrochemical Society, 2016-01-01)
In this study, the electropolymerization of ethyl andmethyl substituted asymmetrical nitrogen analogs of 3,4-ethylenedioxythiophene (OEt and OMe) were synthesized, characterized and their electrochemical properties were investigated. Both polymers (POEt and POMe) were synthesized electrochemically and characterized using spectroelectrochemical technique to determine optical changes of the resulting polymer films. Electrochemical studies demonstrated that these polymers exhibited a significantly low oxidatio...
Synthesis and Characterization of Thiophene and Thieno[3,2-b]thiophene Containing Conjugated Polymers
Rustamh, Elvin; Goker, Seza; UDUM, YASEMİN; Udum, Yasemin Arslan; Toppare, Levent Kamil (The Electrochemical Society, 2015-01-01)
Herein, we report the synthesis of two donor-acceptor-donor polymers (P1 and P2) based on thiophene (M1) and thieno [3,2-b]thiophene (M2) as the donor and 2,5-bis(dodecyloxy)benzene as the acceptor unit. The effects of different donor units on the polymers' electrochemical and optical properties were examined by cyclic voltammetry and spectroelectrochemical analysis. Introducing thieno[3,2-b]thiophene unit as the donor unit enhances pi-stacking and consequently lowering the bandgap of the resulting polymer....
Synthesis and characterization of conducting copolymers of succinic acid bis-(4-pyrrol-1-yl-phenyl) ester and their electrochromic properties
Ertas, M; Çırpan, Ali; Toppare, Levent Kamil (Elsevier BV, 2004-05-07)
A new dipyrrolyl monomer was synthesized via the reaction between 4-pyrrol-1-yl phenol and butanedioyl dichloride. Electrochemical behavior of this monomer, succinic acid bis-(4-pyrrol-1-yl-phenyl) ester (SM) was studied. Homopolymerization was achieved by chemical and constant Current electrolysis methods. Copolymerization of SM with thiophene was performed by constant potential electrolysis in acetonitrile (AN)-tetrabutylammonium tetrafluoroborate (TBAFB) and dichloromethane (DCM)-TBAFB, solvent-electroly...
Citation Formats
S. Eken, B. B. Carbas, A. Akdağ, and A. M. Önal, “Synthesis of New Thienylene Pyrrole Monomers and Their Electropolymerizations,” JOURNAL OF THE ELECTROCHEMICAL SOCIETY, pp. 0–0, 2014, Accessed: 00, 2020. [Online]. Available: