Synthesis and electrochemical polymerization of D-A-D type monomers with thieno [3,4-c] pyrrole-4,6-dione acceptor unit

In this study, three new donor-acceptor-donor type monomers bearing 1,3-dibromo-5-(2-ethylhexyl)-4H-thieno [3,4-c]pyrrole- 4,6(5H)-dione (A) as an acceptor unit and thiophene, 3,4-ethylenedioxythiophene (EDOT) and 3,3-didecy1-3,4-dihydro-2H-thieno[3,4-b][1,4]dioxepine (didecyl-ProDOT) as donor units were synthesized via Stille cross-coupling reaction and their electrochemical polymerization by repetitive cycling was reported. The electrochemical and optical properties of the monomers ((5-(2-ethyl-liexyl)-1,3-di(thienyl-2-yl)-4H-thienolr-3,4-cl pyrrole-4,6(5H)-dione (TAT), 1,3-bis(2,3-dihydrothieno[3,4-1)] (1,4]dioicin-5-yl)-5-(2-ethylhexyl)-4H-thieno(3,4-c) pyrrole-4,6-(5H)-dione (EAE) and 1,3-bis(3,3-didecyl-3,4-dihydro-2H-thieno[3,4-1)111,41-dioxepin-6-yl)-5-(2-ethylhexyl)-4H-thieno[3,4-apyrrole-4,6(5H)-dione (PAP)) and their corresponding polymers called PTAT, PEAE and PPAP were investigated and it was found that EDOT units containing monomer and polymer (EAE and PEAE) have lower oxidation potentials and lower band gap value as compared to didecyl-ProDOT and thiophene units containing monomers and polymers (PAP, TAT and PPAP, PTAT). Spectroelectrochemical investigations conducted on electrochemically obtained polymer films revealed that polymer films exhibited electrochromic behaviors: brick red to gray for PTAT, blue/violet to highly sky blue for PEAE and blue to highly light blue for PPAP in their neutral and oxidized states, respectively. Moreover, PAP was also polymerized chemically using FeC13 as an oxidizing agent. Both chemically and electrochemically obtained PPAP were found to be soluble in some organic solvents and their dichloromethane solutions can be reversibly oxidized and reduced using antimony pentachloride and hydrazine hydrate solutions, respectively.


Effect of fluorine substituted benzothiadiazole on electro-optical properties of donor-acceptor-donor type monomers and their polymers
Çakal, Deniz; Önal, Ahmet Muhtar (Elsevier BV, 2020-11-01)
A series of trimeric monomers bearing thiophene donor units and fluorinated analogues of benzothiadiazole acceptor units was synthesized via donor-acceptor-donor approach and polymerized electrochemically in order to investigate the effect of fluorine atom on electro-optical properties of both monomers and their corresponding polymers. All monomers exhibited solvatochromic and fluorescent properties. The introduction of fluorine atom into the conjugated backbone increased the oxidation potentials. Upon movi...
Electrochemical and optical properties of substituted phthalimide based monomers and electrochemical polymerization of 3,4-ethylenedioxythiophene-polyhedral oligomeric silsesquioxane (POSS) analogue
Çakal, Deniz; Cihaner, Atilla; Önal, Ahmet Muhtar (Elsevier BV, 2019-02-01)
A new series of donor-acceptor-donor type trimeric monomers bearing substituted phthalimide units as acceptor units and thiophene and 3,4-ethylenedioxythiophene (EDOT) as donor units was synthesized and characterized. The strength of acceptor units and intramolecular charge transfer between donor and acceptor units were investigated by using electrochemical and optical methods. The main advantage of phthalimide unit over other acceptor units is the ease of its functionalizability. Thus, utilizing this prope...
Synthesis and characterization of new metal-free and phthalocyanine nickel(II) complex containing macrocyclic moieties
Kantekin, Halit; Rakap, Murat; Gok, Yasar; Sahinbas, Halil Zeki (Elsevier BV, 2007-01-01)
A new metal-free and metallophthalocyanine carrying four 1, 1'-biphenyl crown ether units on peripheral positions have been synthesized. Metal-free phthalocyanine was prepared by the reaction of 2,3-(4',5'-dicyanobenzo)-11,12:13,14-di(1',2'-biphenyl)-1,4,7,10,15,18-hexaoxacycloeicosa-2,11,13-triene with dry 2-(N,N-dimethylamino)ethanol under reflux. Metal derivative of phthalocyanine was also synthesized by the anhydrous NiCl2 and metal-free phthalocyanine in dry quinoline under reflux. The target symmetric...
Synthesis, Characterization and Optoelectrochemical Properties of Poly(2,5-di(thiophen-2-yl)-1-(4-(thiophen-3-yl)phenyl)-1H-pyrrole-co-EDOT)
Turac, Ersen; Sahmetlioglu, Ertugrul; Toppare, Levent Kamil; Yuruk, Huseyin (Informa UK Limited, 2010-01-01)
A new polythiophene derivative was synthesized by electrochemical oxidative polymerization of 2,5-di( thiophen-2-yl)-1-(4-(thiophen-3-yl) phenyl)-1H-pyrrole (TTPP). The structure of the monomer was evaluated by H-1-NMR and FT-IR. The polymer (P(TTPP)) and its co-polymer with 3,4-ethylenedioxythiophene (P(TTPP-co-EDOT)) were synthesized via potentiostatic electrochemical polymerization. The resulting polymers were characterized by cyclic voltammetry (CV), FT-IR, SEM and UV-Vis spectroscopy, and conductivity ...
Synthesis and polymerization of 2-and 3-substituted thiophene derivatives linked by polyether bridges
Tirkeş, Süha; Önal, Ahmet Muhtar (Elsevier BV, 2004-11-15)
New compounds consisting of 2- and 3-thienyl units linked by polyether bridges have been synthesized and their electrochemical polymerization was performed via constant potential electrolysis (CPE) in an electrolytic solution containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF(6)) dissolved in CH3CN. 2-Thienyl monomers (I and II), but not 3-thienyl monomers (III and IV), were also polymerized via chemical oxidation, which yielded broken pi-conjugated polymer products. The polymers were characteri...
Citation Formats
D. Çakal, A. Cihaner, and A. M. Önal, “Synthesis and electrochemical polymerization of D-A-D type monomers with thieno [3,4-c] pyrrole-4,6-dione acceptor unit,” DYES AND PIGMENTS, pp. 175–182, 2018, Accessed: 00, 2020. [Online]. Available: