Synthesis and electrochemical polymerization of diketopyrrolopyrrole based donor-acceptor-donor monomers containing 3,6-and 2,7-linked carbazoles

Three new donor-acceptor-donor (D-A-D) type monomers bearing 2,7- or 3,6-linked carbazoles as the donor unit and 2,5-dihydro-3,6-di-2-thienyl-pyrrolo[3,4-c]pyrrole-1,4-dione (DPP) as the electron poor acceptor unit were synthesized via a Suzuki cross coupling reaction. The monomers were electrochemically polymerized both by repetitive cycling and by constant potential electrolysis in acetonitrile-tetrabutylammonium hexafluorophosphate electrolytic medium containing boron trifluoride diethyl etherate (BFEE). Optical and electrochemical properties of the monomers and their corresponding polymers were investigated and it was found that optical properties show slight variations depending on both the substituent on the nitrogen atom and the linkage site. Monomers, besides reversible oxidations and reversible reduction peaks similar to those present in the differential pulse voltammogram of the acceptor unit, exhibit one irreversible oxidation peak responsible for initiating the electrochemical polymerization of the monomers. Both electrochemical and optical data were used to elucidate the band gap (E-g) values of the polymers and it was found that polymer films obtained from 3,6-linked carbazole derivatives have slightly lower Eg values compared to 2,7-linked derivatives. Furthermore, based on the observed electrochemical behavior of the monomers, a possible mechanism for the electrochemical oxidation was proposed.


Synthesis and electrochemical polymerization of D-A-D type monomers with thieno [3,4-c] pyrrole-4,6-dione acceptor unit
Çakal, Deniz; Cihaner, Atilla; Önal, Ahmet Muhtar (Elsevier BV, 2018-11-01)
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,...
Synthesis and Electrochemical Polymerization of Dithienosilole-Based Monomers Bearing Different Donor Units
Eken, S.; Ergun, E. G. Cansu; Önal, Ahmet Muhtar (The Electrochemical Society, 2016-01-01)
Three new donor-acceptor-donor (DAD) type monomers containing five membered heteroaromatic rings as the donor units and the silicon-bridged bithiophene as the acceptor unit were synthesized via Stille cross-coupling reaction. The monomers, 2,6-di(furan-2-yl)-4,4-dioctyl-4H-silolo[3,2-b:4,5-b'] dithiophene (FSiF), 4,4-dioctyl-2,6-di(thiophen-2-yl)-4H-silolo[3,2-b:4,5-b']dithiophene (TSiT) and 4,4-dioctyl-2,6-di(selenophen-2-yl)-4H-silolo[3,2-b:4,5-b'] dithiophene (SeSiSe) were polymerized electrochemically v...
Synthesis and electrochemical properties of a new benzimidazole derivative as the acceptor unit in donor-acceptor-donor type polymers
OZELCAGLAYAN, Ali Can; SENDUR, Merve; AKBASOGLU, Naime; APAYDIN, Dogukan Hazar; Çırpan, Ali; Toppare, Levent Kamil (2012-04-15)
A new benzimidazole unit, 4'-(tert-butyl)spiro[benzo[d]imidazole-2,1'-cyclohexane] was synthesized and coupled with different donor units like 3-hexylthiophene and 3,4-ethylenedioxythiophene (EDOT) via Stille coupling. The donor-acceptor-donor (D-A-D) type monomers, 4'-(tert-butyl)-4,7-bis(4-hexylthiophen-2-yl)spiro[benzo[d]imidazole-2,1'-cyclohexane] (BIHT) and 4'-(tert-butyl)-4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)spiro[benzo[d]imidazole-2,1'-cyclohexane] (BIED) were electrochemically polymerize...
Synthesis, spectroscopic and electrochemical studies of perylene containing conjugated copolymers
Bayseç, Şebnem; Toppare, Levent Kamil; Yılmaz, Levent; Department of Polymer Science and Technology (2013)
The synthesis , spectroscopic and electrochemical properties of a series of donor-acceptor (DA) type polymers by changing the donor unit (thiophene, dithienopyrrole) polymer backbone were investigated.The synthesized CoP1 and CoP2 were designed to investigate the effect of copolymerization and insertion of perylene tetracarboxylic dimide (PDI) on the structure of benzotriazole (BTz) based polymers. For CoP1 1,7-dibromo-perylene diimide,4,7-dibromo-2-dodecyl-2H-benzo[d][1,2,3]triazole and 2,5 bis(tributylsta...
Synthesis, characterization and photovoltaic properties of benzo[c][1,2,5]oxadiazole based conjugated polymers for organic solar cells
Karakurt, Oğuzhan; Çırpan, Ali; Günbaş, Emrullah Görkem; Department of Chemistry (2021-1-22)
In this thesis, six conjugated polymers were synthesized by coupling of 2,1,3- benzoxadiazole derivatives with donor groups via Stille polycondensation reactions. Moreover, the effect of molecular weight for P1 and P2, effect of position of alkyl chain for P5 and effect of π-bridge groups for P6 which are selenophene and thiophene on optical, electrochemical, and photovoltaic properties were investigated. Also, modifications on alkyl chains of P3 and P4 were performed to increase their functionalities via p...
Citation Formats
M. Akbayrak and A. M. Önal, “Synthesis and electrochemical polymerization of diketopyrrolopyrrole based donor-acceptor-donor monomers containing 3,6-and 2,7-linked carbazoles,” POLYMER CHEMISTRY, pp. 6110–6119, 2016, Accessed: 00, 2020. [Online]. Available: