- Synthetic control of structural order in N-alkylthieno[3,4- c ]pyrrole-4,6-dione-based polymers for efficient solar cells
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The correlation between the nature of alkyl substituents on N-alkylthieno[3,4-c]pyrrole-4,6-dione (TPD)-based polymers and solar cell device performance has been investigated. After adjusting device parameters, these TPD-based polymers used with PC61BM provided photovoltaic responses ranging from 4.0% to 6.8%, depending on the size and shape of the alkyl solubilizing groups. Further, we have correlated the effect of the alkyl groups on the structural order and orientation of the polymer backbone using grazing incidence X-ray scattering analysis, and we have demonstrated how fine-tuning of these parameters can improve the power conversion efficiency.
- Piliego, Claudia,Holcombe, Thomas W.,Douglas, Jessica D.,Woo, Claire H.,Beaujuge, Pierre M.,Frechet, Jean M. J.
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- Synthesis, characterization, and photovoltaic property of a low band gap polymer alternating dithienopyrrole and thienopyrroledione units
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The lower the highest occupied molecular orbital (HOMO) energy level of the conjugated polymer is, the higher the open-circuit voltage (VOC) of the obtained polymer solar cell (PSC) is. To achieve this goal, a new conjugated polymer (PDTPTPD) alternating dithienopyrrole (DTP) and thienopyrroledione (TPD) units was designed and synthesized by Stille coupling reaction. Through UV-vis absorption and cyclic voltammetry (CV) measurements, it was found that the resulting copolymer exhibited both a low optical band gap of 1.62 eV and a low HOMO energy level of -5.09 eV owing to the electronegativity of TPD moiety. Preliminary photovoltaic study disclosed that the PSC based on PDTPTPD:PCBM ([6,6]-phenyl-C61 butyric acid methyl ester) blend showed a power conversion efficiency (PCE) of 1.9%, with a VOC of 0.70 V, and a short circuit current (ISC) of 6.97 mA/cm2, suggesting that PDTPTPD is a promising photovoltaic polymer.
- Hu, Xiaolian,Shi, Minmin,Zuo, Lijian,Nan, Yaxiong,Liu, Yujing,Fu, Lei,Chen, Hongzheng
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- Copper-catalyzed direct C-H arylation of thieno[3,4-c]pyrrole-4,6-dione (TPD): Toward efficient and low-cost synthesis of ??-functional small molecules
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A series of thieno[3,4-c]pyrrole-4,6-dione (TPD)-based functional small molecules were efficiently synthesized through direct C-H arylations using inexpensive copper salts. In this study, we examined all required reaction parameters including various copper complexes, ligands, bases, and (co)-solvents. Under the optimum reaction conditions, the C-H arylation proceeded smoothly and a variety of functional groups such as ester, nitrile, fluoride, chloride, triazene, and amine were tolerated. This method provides a step-economical and relatively low-cost synthetic alternative to presently used coupling reactions for the preparation of TPD-containing p-functional materials.
- Song, Yi-Ting,Lin, Po-Han,Liu, Ching-Yuan
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- Poly(5-alkyl-thieno[3,4-: C] pyrrole-4,6-dione): A study of π-conjugated redox polymers as anode materials in lithium-ion batteries
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Organic polymers have been investigated as active electrode materials in the past few years and although materials with high energy density and tunable redox potential have been developed, their dissolution into the electrolyte and their low electronic conductivity compromised their use in rechargeable batteries. To overcome these drawbacks, seven n-type π-conjugated redox polymers based on 5-alkyl-thieno[3,4-c]pyrrole-4,6-dione have been developed for anode materials of rechargeable batteries. The role of the carbonyl group on the electrochemical activity of these polymers has been demonstrated and the effect of the alkyl chain and the comonomer unit on their electrochemical performance. The redox potential of the polymer has been shown to vary over a range of 400 mV and a polymer with a suitable redox potential of 1.55 V vs. Li/Li+ for an anode of a lithium-ion battery has been found.
- Robitaille, Amélie,Perea, Alexis,Bélanger, Daniel,Leclerc, Mario
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- Synthesis of TPD–thiophene-based small molecule donor for organic photovoltaic cells
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The donor–acceptor–donor (D–A–D) type small molecule, TPD2T, was synthesized by the Stille coupling reaction and consisted of the electron-withdrawing thiene[3,4-c]pyrrole-4,6-dione (TPD) unit as an electron-accepting (A) core and electron-rich bithiophene units as electron-donating (D) groups. The absorption maximum of the TPD2T film was observed at 460?nm, and was broader and red-shifted compared to that in solution (λmax = 450?nm). Organic photovoltaic cells fabricated with the conventional and inverted structures both exhibited similar power conversion efficiencies of 0.14–0.15%. Despite the low short-circuit current values, the TPD2T devices showed high open-circuit voltages of over 1.0?V owing to the relatively low-lying HOMO level of TPD2T (?5.4?eV).
- Lim, Eunhee
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- Thieno-, furo-, and selenopheno[3,4-c ]pyrrole-4,6-dione copolymers: Effect of the heteroatom on the electrooptical properties
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New push-pull conjugated polymers based on furo[3,4-c]pyrrole-4,6-dione (FPD) and selenopheno[3,4-c]pyrrole-4,6-dione (SePD) have been synthesized and compared with their thieno[3,4-c]pyrrole-4,6-dione (TPD) analogues to investigate the effects of the heteroatom on the electrooptical properties. The copolymers were synthesized using either Stille cross-coupling or direct heteroarylation polymerization (DHAP), the latter method giving high molecular weights. Hypsochromic shifts of the band gaps were observed for FPD-based copolymers (sulfur substituted by oxygen) while small bathochromic shift was observed for SePD (sulfur substituted by selenium) when compared to its TPD analogue. These two new classes of conjugated polymers exhibit electrooptical properties that could lead to interesting bulk heterojunction plastic solar cells.
- Beaupre, Serge,Pron, Agnieszka,Drouin, Simon H.,Najari, Ahmed,Mercier, Lauren G.,Robitaille, Amelie,Leclerc, Mario
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- Synthesis and characterization of new thieno[3,4-c]pyrrole-4,6-dione derivatives for photovoltaic applications
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A new class of low-bandgap copolymers based on benzodithiophene (BDT) and thieno[3,4-c]pyrrole-4,6-dione (TPD) units is reported. Chemical modifications of the conjugated backbone promote both high molecular weights and processability while allowing for tuning of the electronic properties. Copolymers with substituted thiophene spacers (alkyl chains facing the BDT unit) or unsubstituted thiophene spacers tend to have low power conversion efficiencies (PCE less than 1%) due to a bad morphology of the active layer, whereas copolymers with substituted thiophene spacers (alkyl chains facing TPD unit) show enhanced morphology and PCEs up to of 3.9%. Finally, BDT-TPD copolymers without any thiophene spacers still show the best performances with power conversion efficiencies up to 5.2%. The synthesis and characterization of new electroactive and photoactive copolymers based on benzodithiophene (BDT) and thieno[3,4-c]pyrrole-4,6-dione (TPD) units are described. The copolymers are synthesized with or without thiophene spacers in order to tune the electronic properties and to control the morphology of the active layer in bulk heterojunction solar cells. The potential of these new materials in photovoltaic devices is investigated.
- Najari, Ahmed,Beaupre, Serge,Berrouard, Philippe,Zou, Yingping,Pouliot, Jean-Remi,Lepage-Perusse, Charlotte,Leclerc, Mario
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- Synthesis, characterization and photovoltaic properties of dithienobenzodithiophene-based conjugated polymers
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Two new donor-acceptor typed conjugated polymers (P1 and P2) based on the large coplanar and more-extended donor dithieno[2,3-d:2,3-d′]benzo[1,2-b:4,5-b′]dithiphene and thienopyrroledione (TPD) units were synthesized. P1 and P2 have the same polymer backbone, but with different side chains, where P1 has 2-ethylhexyl side chains and P2 has the longer branched 4-ethyoctyl side chains. The solubility measurements show that P2 with longer branched 4-ethyloctyl side chain has better solubility in organic solvents than that of P1. The optical, electrochemical and photovoltaic properties were investigated. P1 and P2 show the very same absorption features in both solution and film states indicating an enhanced molecular planarity of the polymer chains in P1 and P2, which benefits from the large coplanar dithieno[2,3-d:2,3-d′]benzo[1,2-b:4,5-b′]dithiphene unit. The band-gaps of P1 and P2 are at 1.83?eV and 1.74?eV, respectively. The solar cells with P1 or P2 as the electron donor component and PC71BM as the electron acceptor were fabricated and measured under AM 1.5G illumination at 100?mW?cm?2. The results show that the P2/PC71BM-based device showed a moderate power conversion efficiency of 2.86%, which is ~50% improvement in comparison with P1/PC71BM-based device.
- Lang, Caili,Fan, Jingzhe,Gao, Yueyue,Liu, Ming,Zhang, Yong,Guo, Fengyun,Zhao, Liancheng
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- Structural Insight into Aggregation and Orientation of TPD-Based Conjugated Polymers for Efficient Charge-Transporting Properties
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In this study, we obtained a new structural insight into the charge-transporting properties in TPD-based polymers that cannot be solely explained in terms of the type of orientation. We synthesized two types of copolymers comprising mono-TPD or bis-TPD as the accepting unit. Although the planarity and energy levels are similar with the mono-TPD unit, the aggregation state is quite different, and the X-aggregation tendency seems to be stronger when the bis-TPD unit is incorporated. In the case of TPD1, an effective π-πorbital overlap is found to originate from the H-aggregates, and 3D charge transport pathways are formed with a bimodal orientation of edge-on and face-on, resulting in an efficient charge transportation (1.84 cm2·V-1·s-1 of hole and 0.31 cm2·V-1·s-1 of electron). In contrast, despite the well-aligned edge-on orientation of TPD2, it exhibited a relatively very low mobility and splitted emission characteristics in photoluminescence spectra because of the tilted intermolecular stacking pattern with an X-shape (0.015 cm2·V-1·s-1 for hole and 0.16 cm2·V-1·s-1 for electron). An overall characterization of the semiconducting polymers was performed, and it was found that the type of aggregation in the final thin films, such as H- or X-aggregation, is indeed important and perhaps more important than the orientation to obtain polymers with a high charge carrier mobility.
- Lim, Dae-Hee,Kim, Yeon-Ju,Kim, Yeong-A,Hwang, Kyoungtae,Park, Jong-Jin,Kim, Dong-Yu
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p. 4629 - 4638
(2019/05/08)
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- Pd-catalyzed direct C-H arylation of thieno[3,4-c]pyrrole-4,6-dione (TPD): A step-economical synthetic alternative to access TPD-centred symmetrical small molecules
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We demonstrate a step-economical and viable synthetic alternative to access a series of thieno[3,4-c]pyrrole-4,6-dione (TPD)-based π-conjugated molecules through Pd-catalyzed direct C-H arylations. A comprehensive synthetic study including the screening of various kinds of palladium catalysts, ligands, and bases is reported. Under the optimum reaction conditions, TPD and its common derivatives underwent efficient and mild direct C-H arylations with a variety of functionalized bromoarenes. Functional groups such as ester, nitrile, ketone, aldehyde, and halide were well-tolerated, which substantially extended the reaction scope. We hope the reported method will provide materials scientists a relatively greener synthetic route to efficiently prepare TPD-containing π-functional materials. This journal is the Partner Organisations 2014.
- Chang, Shan-Yun,Lin, Po-Han,Liu, Ching-Yuan
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p. 35868 - 35878
(2014/11/07)
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- THIENO, FURO AND SELENOPHENO-[3,4-C]PYRROLE-4,6-DIONE COPOLYMERS
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Novel photoactive copolymers based on thieno, furo or selenopheno-[3,4- c]pyrrole-4,6-dione-derivative are described herein. More specifically, the photoactive copolymers comprise repeating units of Formula I -[A1-A2]- I wherein A1 is an electron donating unit such as a mono or polycyclic heteroaryl that is unsubstitued or substituted with one or more C1-20-alkyl or C1-20-alkoxy; and A2 is an alkylfuro or alkylselenopheno-[3,4-c]pyrrole-4,6-dione-derivative. The photoactive copolymers are suitable for use in BHJ solar cells.
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Paragraph 00111
(2014/03/25)
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- Enhanced performance of quasi-solid-state dye-sensitized solar cells by branching the linear substituent in sensitizers based on thieno[3,4-c]pyrrole-4, 6-dione
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Thieno[3,4-c]pyrrole-4,6-dione-based organic sensitizers with triphenylamine (FNE38 and FNE40) or julolidine (FNE39 and FNE41) as electron-donating unit have been designed and synthesized. A linear hexyl group or a branched alkyl chain, the 2-ethylhexyl group, is incorporated into molecular skeleton of the dyes to minimize intermolecular interactions. The absorption, electrochemical, and photovoltaic properties for these sensitizers were then systematically investigated. It is found that the sensitizers have similar photophysical and electrochemical properties, such as absorption spectra and energy levels, owing to their close chemical structures. However, the quasi-solid-state dye-sensitized solar cells (DSSCs) based on the two types of sensitizers exhibit very different performance parameters. Upon the incorporation of the short ethyl group on the hexyl moiety, enhancements in both open-circuit voltage (Voc) and short-circuit current (J sc) are achieved for the quasi-solid-state DSSCs. The Voc gains originating from the suppression of charge recombination were quantitatively investigated and are in good agreement with the experimentally observed Voc enhancements. Therefore, an enhanced solar energy conversion efficiency (I·) of 6.16 %, constituting an increase by 23 %, is achieved under standard AM 1.5 sunlight without the use of coadsorbant agents for the quasi-solid-state DSSC based on sensitizer FNE40, which bears the branched alkyl group, in comparison with that based on FNE38 carrying the linear alkyl group. This work presents a design concept for considering the crucial importance of the branched alkyl substituent in novel metal-free organic sensitizers. Copyright
- Feng, Quanyou,Zhang, Weiyi,Zhou, Gang,Wang, Zhong-Sheng
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p. 168 - 177
(2013/02/25)
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