- From-core and from-end direct C-H arylations: A step-saving new synthetic route to thieno[3,4-c]pyrrole-4,6-dione (TPD)-incorporated D-π-A-π-D functional oligoaryls
-
In contrast to the traditional multistep synthesis, herein an efficient and fewer-steps new synthetic strategy is demonstrated for the facile preparation of organic-electronically important D-π-A-π-D-type oligoaryls through sequential direct C-H arylations. This methodology has shown that the synthesis of thieno[3,4-c]pyrrole-4,6-dione (TPD)- or furano[3,4-c]pyrrole-4,6-dione (FPD)-centred target molecules could be accessed step-economically either from the core structure (acceptor) or from the end structure (donor), which supplied a more flexible and succinct new synthetic alternative to the preparation of the π-functional small-molecule semiconducting materials. In addition, optical and electrochemical properties of the synthesized oligoaryls were examined.
- Lin, Po-Han,Liu, Kuan-Ting,Liu, Ching-Yuan
-
-
Read Online
- Proaromatic pyranylidene chalcogen analogues and cyclopenta[c]thiophen-4,6-dione as electron donors and acceptor in efficient charge-transfer chromophores
-
Fifteen new push-pull chromophores based on a proaromatic pyranylidene donor and its chalcogen analogues and various electron acceptor moieties were synthesized in a straightforward manner. These model molecules were designed and prepared to investigate the concept of proaromaticity as a tool to tune the fundamental properties of push-pull systems. All target chromophores with systematically varied structure were further investigated by electrochemistry, absorption spectra, and EFISH experiment in conjunction with DFT calculations. Employing structural variations such as chalcogen/acceptor replacement, extension of the π-system, and the position of substitution along the pyran ring, the HOMO-LUMO gap can be tuned within the range of 2.18 to 1.41?eV. A new and powerful electron withdrawing moiety, combining features of polarizable thiophene and successful indane-1,3-dione acceptor, cyclopenta[c]thiophen-4,6-dione (ThDione) has also been developed.
- Solanke, Parmeshwar,Achelle, Sylvain,Cabon, Nolwenn,Pytela, Old?ich,Barsella, Alberto,Caro, Bertrand,Robin-le Guen, Fran?oise,Podlesny, Jan,Klikar, Milan,Bure?, Filip
-
-
Read Online
- Ring opening of 2,5-didehydrothiophene: Matrix photochemistry of C 4H2S isomers
-
Irradiation (λ > 254 nm) of matrix-isolated 2,5-diiodothiophene (10) gives rise to IR bands assigned to ethynylthioketene (6). Diethynyl sulfide (3), which would form in the process of retro-Bergman cyclization of the incipient 2,5-didehydrothiophene (4), is not detected. Under the same irradiation conditions, matrix-isolated diethynyl sulfide (3) rearranges to thioketene 6 and butatrienethione (5), the global minimum on C4H 2S potential energy surface. The photochemical formation of thioketene 6 from either diyl 4 or sulfide 3 may be interpreted in line with a recent computational prediction on the thermal ring opening of diyl 4, which favors C-S bond cleavage, leading to 6, over C-C bond cleavage, leading to 3. Photolysis of matrix-isolated 3,4-thiophenedicarboxylic acid anhydride (11) enables the observation of the photoequilibration of three low-energy C 4H2S isomers, butatrienethione (5), ethynylthioketene (6), and butadiynylthiol (7), via apparent [1,3]-hydrogen shifts.
- Kim, Yong Seol,Inui, Hiroshi,McMahon, Robert J.
-
-
Read Online
- A Distannylated Monomer of a Strong Electron-Accepting Organoboron Building Block: Enabling Acceptor–Acceptor-Type Conjugated Polymers for n-Type Thermoelectric Applications
-
Acceptor–acceptor (A-A) copolymerization is an effective strategy to develop high-performance n-type conjugated polymers. However, the development of A-A type conjugated polymers is challenging due to the synthetic difficulty. Herein, a distannylated monomer of strong electron-deficient double B←N bridged bipyridine (BNBP) unit is readily synthesized and used to develop A-A type conjugated polymers by Stille polycondensation. The resulting polymers show ultralow LUMO energy levels of ?4.4 eV, which is among the lowest value reported for organoboron polymers. After n-doping, the resulting polymers exhibit electric conductivity of 7.8 S cm?1 and power factor of 24.8 μW m?1 K?2. This performance is among the best for n-type polymer thermoelectric materials. These results demonstrate the great potential of A-A type organoboron polymers for high-performance n-type thermoelectrics.
- Deng, Sihui,Dong, Changshuai,Liu, Jun,Meng, Bin,Wang, Lixiang
-
-
Read Online
- Chemoselective Electrosynthesis Using Rapid Alternating Polarity
-
Challenges in the selective manipulation of functional groups (chemoselectivity) in organic synthesis have historically been overcome either by using reagents/catalysts that tunably interact with a substrate or through modification to shield undesired sites of reactivity (protecting groups). Although electrochemistry offers precise redox control to achieve unique chemoselectivity, this approach often becomes challenging in the presence of multiple redox-active functionalities. Historically, electrosynthesis has been performed almost solely by using direct current (DC). In contrast, applying alternating current (AC) has been known to change reaction outcomes considerably on an analytical scale but has rarely been strategically exploited for use in complex preparative organic synthesis. Here we show how a square waveform employed to deliver electric current - rapid alternating polarity (rAP) - enables control over reaction outcomes in the chemoselective reduction of carbonyl compounds, one of the most widely used reaction manifolds. The reactivity observed cannot be recapitulated using DC electrolysis or chemical reagents. The synthetic value brought by this new method for controlling chemoselectivity is vividly demonstrated in the context of classical reactivity problems such as chiral auxiliary removal and cutting-edge medicinal chemistry topics such as the synthesis of PROTACs.
- Baran, Phil S.,Carlson, Ethan,Edwards, Jacob T.,Hayashi, Kyohei,Kawamata, Yu,Saito, Masato,Shaji, Shobin,Simmons, Bryan J.,Waldmann, Dirk,Zapf, Christoph W.
-
supporting information
p. 16580 - 16588
(2021/10/20)
-
- CRYSTAL FORMS OF THIOPHENE DERIVATIVES
-
Disclosed is crystal form I of compound (S)—N-[5-[1-(3-ethoxy-4-methoxyphenyl)-2-(methylsulfonyl)ethyl]-4,6-dioxo-5,6-dihydro-4H-thieno[3,4-c]pyrrole-1-yl]acetamide.
- -
-
Paragraph 0274
(2021/05/14)
-
- PDE4 INHIBITORS, PHARMACEUTICAL COMPOSITIONS, AND THERAPEUTIC APPLICATIONS
-
Provided herein are phosphodiesterase 4 (PDE4) inhibitors, e.g., a compound of Formula (I) or (II), and pharmaceutical compositions thereof. Also provided herein are methods of their use for treating, preventing, or ameliorating one or more symptoms of a disease, disorder, or condition associated with PDE4 malfunction.
- -
-
Paragraph 0235
(2021/06/22)
-
- From Red to Green Luminescence via Surface Functionalization. Effect of 2-(5-Mercaptothien-2-yl)-8-(thien-2-yl)-5-hexylthieno[3,4- c]pyrrole-4,6-dione Ligands on the Photoluminescence of Alloyed Ag-In-Zn-S Nanocrystals
-
A semiconducting molecule containing a thiol anchor group, namely 2-(5-mercaptothien-2-yl)-8-(thien-2-yl)-5-hexylthieno[3,4-c]pyrrole-4,6-dione (abbreviated as D-A-D-SH), was designed, synthesized, and used as a ligand in nonstoichiometric quaternary nanocrystals of composition Ag1.0In3.1Zn1.0S4.0(S6.1) to give an inorganic/organic hybrid. Detailed NMR studies indicate that D-A-D-SH ligands are present in two coordination spheres in the organic part of the hybrid: (i) inner in which the ligand molecules form direct bonds with the nanocrystal surface and (ii) outer in which the ligand molecules do not form direct bonds with the inorganic core. Exchange of the initial ligands (stearic acid and 1-aminooctadecane) for D-A-D-SH induces a distinct change of the photoluminescence. Efficient red luminescence of nanocrystals capped with initial ligands (λmax = 720 nm, quantum yield = 67%) is totally quenched and green luminescence characteristic of the ligand appears (λmax = 508 nm, quantum yield = 10%). This change of the photoluminescence mechanism can be clarified by a combination of electrochemical and spectroscopic investigations. It can be demonstrated by cyclic voltammetry that new states appear in the hybrid as a consequence of D-A-D-SH binding to the nanocrystals surface. These states are located below the nanocrystal LUMO and above its HOMO, respectively. They are concurrent to deeper donor and acceptor states governing the red luminescence. As a result, energy transfer from the nanocrystal HOMO and LUMO levels to the ligand states takes place, leading to effective quenching of the red luminescence and appearance of the green one.
- Kowalik, Patrycja,Bujak, Piotr,Wróbel, Zbigniew,Penkala, Mateusz,Kotwica, Kamil,Maroń, Anna,Pron, Adam
-
supporting information
p. 14594 - 14604
(2020/10/09)
-
- Structural Insight into Aggregation and Orientation of TPD-Based Conjugated Polymers for Efficient Charge-Transporting Properties
-
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
-
p. 4629 - 4638
(2019/05/08)
-
- Regulating exciton bonding energy and bulk heterojunction morphology in organic solar cells: Via methyl-functionalized non-fullerene acceptors
-
Electron-deficient end groups (EGs) are very important for non-fullerene small molecule acceptors (NF-SMAs) to tune their absorption, energy levels, and crystallization properties. Herein, we designed and synthesized three SMAs, namely, BTTIC-0M, BTTIC-2M, and BTTIC-4M by adding the methyl unit into 2-(6-oxo-5,6-dihydro-4H-cyclopenta[c]thiophen-4-ylidene)malononitrile (CPTCN). Methyl group, with its slight electron-donating ability, significantly elevates the LUMO energy levels but does not seriously affect the bandgaps of the CPTCN-based SMAs, which helps to reduce the energy loss (Eloss). In-depth dynamic theoretical simulations of the donor-acceptor (D-A) complex reveal that the exciton bonding energy (BE) can be fine-tuned by continuously increasing the methyl groups on the end groups of the SMAs. Methyl-substituted EG reduces the driving force and also enhances the BE of the charge transport (CT) state exciton, leading to a decrease in the exciton dissociation efficiencies. However, we found that one methyl-functionalized CPTCN enables PBDB-T:BTTIC-2M-based organic solar cells (OSCs) to achieve a power conversion efficiency (PCE) as high as 13.15%. Though PBDB-T:BTTIC-2M-based OSCs exhibit a slightly lower exciton dissociation efficiency than those of PBDB-T:BTTIC-0M, a more favorable superficial and internal morphology is attained in the PBDB-T:BTTIC-2M bulk-heterojunction layer, which balances the electron and hole mobilities and diminishes the bimolecular recombination. Comparatively, BTTIC-4M failed to realize a high performance owing to its adverse interactions with the polymer chain and the multiscale phase separation in the blend films. Actually, adjusting the number of methyl groups on the end group is done to compensate the current-voltage losses within the OSC devices with complicated contributions from absorption spectra, LUMO energy levels, exciton bonding energies, and morphologies.
- Gao, Wei,Liu, Tao,Luo, Zhenghui,Zhang, Lin,Ming, Ruijie,Zhong, Cheng,Ma, Wei,Yan, He,Yang, Chuluo
-
p. 6809 - 6817
(2019/03/26)
-
- Achieving high short-circuit current and fill-factor via increasing quinoidal character on nonfullerene small molecule acceptor
-
Recently, the fused-ring based low band gap (LBG) small molecule acceptors (SMAs) have emerged as efficient nonfullerene acceptors. So far, these LBG SMAs are mainly designed with IC (2-methylene-(3-(1,1-dicyanomethylene)indanone)) or its analogs, the benzo-type electron-accepting (A) units. Compared to benzene, thiophene is less aromatic and thus the thiophene-involving semiconducting molecule has more quinoidal character, which effectively reduces the energy gap between the highest occupied molecular orbit (HOMO) and the lowest unoccupied molecular orbit (LUMO). Herein, we show that replacing the IC units in ITIC with the CT (cyclopenta[c]thiophen-4-one-5-methylene-6-(1,1-dicyanomethylene)), a thiophene-fused A unit, the quinoidal character is enhanced from 0.0353 on ITIC to 0.0349 on ITCT, the CT-ended SMA. The increase in the quinoidal character reduces the optical band gap and enhances the near IR absorptivity. When blended with the wide band gap (WBG) polymer donor, PBDB-T, an average power conversion efficiency of 10.99% is obtained with a short-circuit current-density (Jsc) of 17.88 mA/cm2 and a fill-factor (FF) of 0.723. For comparisons, the Jsc is of 16.92 mA/cm2, FF is of 0.655 and PCE is of 9.94% obtained from the ITIC:PBDB-T device. This case indicates that the replacement of the benzene ring on the IC unit with a more polarizable five-member ring such as thiophene is an effective way to enhance the absorption of the near IR solar photons towards designing high-performance nonfullerene polymer solar cells.
- Liu, Wenxu,Li, Weiping,Yao, Jiannian,Zhan, Chuanlang
-
supporting information
p. 381 - 384
(2017/12/04)
-
- BICYLIC COMPOUNDS AND METHODS OF USE
-
The present invention provides compounds that modulate protein function, specifically phosphodiesterase 4 (PDE4). The invention provides methods of treating, ameliorating, and/or preventing diseases, disorders, and conditions associated with PDE4. Compositions, including in combination with other inflammatory mediators, are also provided.
- -
-
Paragraph 0208
(2019/01/04)
-
- Fluorination in thieno[3,4-: C] pyrrole-4,6-dione copolymers leading to electron transport, high crystallinity and end-on alignment
-
A series of copolymers based on thieno[3,4-c]pyrrole-4,6-dione and thiophene-phenyl-thiophene with varying degrees of fluorination on the phenyl unit was synthesized by Stille polycondensation. The influence of the degree of fluorination on the optical, thermal and electrochemical properties of these polymers is systematically studied. Additionally, the charge transport in organic field effect transistors (OFETs) as well as the thin film alignment are investigated. After thermal annealing the non-fluorinated as well as difluorinated polymers show ambipolar charge transport in OFETs. In contrast, tetrafluorination results in exclusively n-type behaviour with an electron mobility of 3.7 × 10-4 cm2 V-1 s-1. GIWAXS measurements of as-cast and annealed films reveal a very interesting structural alignment in thin films. All polymers show the rarely observed "end-on" orientation, where the polymer chains stand on the substrate. This may be explained by the low molecular weights of these polymers in relation to the film thickness. Fluorination does not influence the microstructural properties, only the propensity of crystallization is increased.
- Weller,Breunig,Mueller,Gann,McNeill,Thelakkat
-
supporting information
p. 7527 - 7534
(2017/08/16)
-
- 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
-
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
-
supporting information
p. 18088 - 18094
(2017/09/08)
-
- Design, synthesis and electronic properties of push-pull-push type dye
-
A Sonogashira cross-coupling protocol was employed for the construction of a push-pull-push type dye. An ethynyl π-spacer extends the effective π-conjugation length between push and pull units without altering the planarity of the electron donor/acceptor pair. The variation of the strength of the alkyne π-spacer electron push (or donor) units of these dyes has a strong effect on the shifting of both absorption and emission maxima and thereby on the Stokes shift. The dyes were solvatochromic and their solvatochromicity was highly dependent on the electron push unit. Strong red shifted emissions were likely to arise due to the internal charge transfer (ICT) from the electron push unit to the electron pull unit. Calculated energy values of HOMO → LUMO transitions are in good accordance with experimental observations. Alkyne conjugated electron push units (-CC-Ar; Ar = Ph, Ph-OMe, Ph-NMe2) are more effective to increase the EHOMO levels. Overall, experimental and theoretical results of the push-pull-push dyes indicate that they can be used as promising conjugated materials with predictable electronic properties for optoelectronic devices.
- Kundu, Rajen,Kulshreshtha, Chandramouli
-
p. 77460 - 77468
(2015/09/28)
-
- 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
-
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
-
p. 35868 - 35878
(2014/11/07)
-
- 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
-
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
-
supporting information
p. 3761 - 3768
(2015/02/19)
-
- Langmuir-blodgett films of amphiphilic thieno[3,4- c ]pyrrole-4,6-dione- based alternating copolymers
-
The synthesis of four amphiphilic thieno[3,4-c]pyrrole-4,6-dione (TPD)-based alternating copolymers and their behavior at the air-water interface are reported. Homogeneous and stable monolayers of TPD-based copolymers were prepared. Brewster angle microscopy (BAM) was utilized to characterize the morphology and topography of these Langmuir films. UV-vis absorption spectroscopy as well as atomic force microscopy has revealed a regular transfer of some copolymers on glass substrates. It was possible to obtain homogeneous Langmuir-Blodgett films of up to 30 layers. Infrared dichroic measurements revealed an edge-on orientation. These Langmuir-Blodgett films made of conjugated polymers are therefore good candidates for organic field-effect transistors (OFETs).
- Ouattara, Mariane Perpethue,Lenfant, Stephane,Vuillaume, Dominique,Pezolet, Michel,Rioux-Dube, Jean-Francois,Brisson, Josee,Leclerc, Mario
-
p. 6408 - 6418
(2013/09/23)
-
- A versatile approach to organic photovoltaics evaluation using white light pulse and microwave conductivity
-
State-of-the-art low band gap conjugated polymers have been investigated for application in organic photovoltaic cells (OPVs) to achieve efficient conversion of the wide spectrum of sunlight into electricity. A remarkable improvement in power conversion efficiency (PCE) has been achieved through the use of innovative materials and device structures. However, a reliable technique for the rapid screening of the materials and processes is a prerequisite toward faster development in this area. Here we report the realization of such a versatile evaluation technique for bulk heterojunction OPVs by the combination of time-resolved microwave conductivity (TRMC) and submicrosecond white light pulse from a Xe-flash lamp. Xe-flash TRMC allows examination of the OPV active layer without requiring fabrication of the actual device. The transient photoconductivity maxima, involving information on generation efficiency, mobility, and lifetime of charge carriers in four well-known low band gap polymers blended with phenyl-C61-butyric acid methyl ester (PCBM), were confirmed to universally correlate with the PCE divided by the open circuit voltage (PCE/Voc), offering a facile way to predict photovoltaic performance without device fabrication.
- Saeki, Akinori,Yoshikawa, Saya,Tsuji, Masashi,Koizumi, Yoshiko,Ide, Marina,Vijayakumar, Chakkooth,Seki, Shu
-
supporting information
p. 19035 - 19042
(2013/01/15)
-
- THIOPHENE DERIVATIVES
-
Disclosed is a compound of formula (1), wherein R1, R2, R3, R4, R5, R6, R7 and R8 are as defined in the present application.
- -
-
Page/Page column 26
(2012/04/17)
-
- Synthesis and photovoltaic properties of thieno[3,4-c]pyrrole-4,6-dione- based donor-acceptor Copolymers
-
Three donor-acceptor (D-A) 1,3-di(thien-2-yl)thieno [3,4-c]pyrrole-4,6- dione-based copolymers, poly{9,9-dioctylfluorene-2,7-diyl-alt-1,3-bis(4- hexylthien-2-yl)-5-octylthieno[3,4-c]pyrrole-4,6-dione}, poly{N-(1-octylnonyl) carbazole-2,7-diyl-alt-1,3-bis(4-hexylthien-2-yl)-5-octylthieno[3,4-c]pyrrole-4, 6-dione}, and poly {4,8-bis(2-ethylhexyloxyl) benzo[1,2-b:3,4-b']dithiophene- alt-1,3-bis(4-hexylthien-2-yl)-5-octylthieno[3,4-c] pyrrole-4,6-dione} were synthesized by Suzuki or Stille coupling reaction. By changing the donor segment, the bandgaps and energy levels of these copolymers could be finely tuned. Cyclic voltammetric study shows that the highest occupied molecular orbital (HOMO) energy levels of the three copolymers are deep-lying, which implies that these copolymers have good stability in the air and the relatively low HOMO energy level assures a higher open-circuit potential when they are used in photovoltaic cells. Bulk-heterojunction photovoltaic cells were fabricated with these polymers as the donors and PC71BM as the acceptor. The cells based on the three copolymers exhibited power conversion efficiencies of 0.22, 0.74, and 3.11% with large open-circuit potential of 1.01, 0.99, and 0.90 V under one sun of AM 1.5 solar simulator illumination (100 mW/cm2).
- Wen, Shanpeng,Cheng, Weidong,Li, Pengfei,Yao, Shiyu,Xu, Bin,Li, Hui,Gao, Yajun,Wang, Zilong,Tian, Wenjing
-
experimental part
p. 3758 - 3766
(2012/09/22)
-
- Thieno[3,4- c ]pyrrole-4,6-dione-based polymer semiconductors: Toward high-performance, air-stable organic thin-film transistors
-
We report a new p-type semiconducting polymer family based on the thieno[3,4-c]pyrrole-4,6-dione (TPD) building block, which exhibits good processability as well as good mobility and lifetime stability in thin-film transistors (TFTs). TPD homopolymer P1 was synthesized via Yamamoto coupling, whereas copolymers P2-P8 were synthesized via Stille coupling. All of these polymers were characterized by chemical analysis as well as thermal analysis, optical spectroscopy, and cyclic voltammetry. P2-P7 have lower-lying HOMOs than does P3HT by 0.24-0.57 eV, depending on the donor counits, and exhibit large oscillator strengths in the visible region with similar optical band gaps throughout the series (~1.80 eV). The electron-rich character of the dialkoxybithiophene counits in P8 greatly compresses the band gap, resulting in the lowest Egopt in the series (1.66 eV), but also raising the HOMO energy to -5.11 eV. Organic thin-film transistor (OTFT) electrical characterization indicates that device performance is very sensitive to the oligothiophene conjugation length, but also to the solubilizing side chain substituents (length, positional pattern). The corresponding thin-film microstructures and morphologies were investigated by XRD and AFM to correlate with the OTFT performance. By strategically varying the oligothiophene donor conjugation length and optimizing the solubilizing side chains, a maximum OTFT hole mobility of ~0.6 cm2 V-1 s-1 is achieved for P4-based devices. OTFT environmental (storage) and operational (bias) stability in ambient was investigated, and enhanced performance is observed due to the low-lying HOMOs. These results indicate that the TPD is an excellent building block for constructing high-performance polymers for p-type transistor applications due to the excellent processability, substantial hole mobility, and good device stability.
- Guo, Xugang,Ortiz, Rocio Ponce,Zheng, Yan,Kim, Myung-Gil,Zhang, Shiming,Hu, Yan,Lu, Gang,Facchetti, Antonio,Marks, Tobin J.
-
scheme or table
p. 13685 - 13697
(2011/10/09)
-
- DIOXYPYRROLO-HETEROAROMATIC COMPOUNDS AND ORGANIC ELECTRONIC DEVICES USING THE SAME
-
The present invention relates to dioxypyrrolo-heterocyclic compounds and an organic electronic device using the same. The compound of the present invention satisfies the requirements for use in an organic electronic device such as an organic light emitting device, an organic thin film transistor, and an organic solar cell, for example, suitable energy levels, and the electrochemical and thermal stability, by introducing various substituents to the core structure, and also have amorphous or crystalline property depending on the Mnd of the substituents, to satisfy the characteristics individually required for each of the devices. Further, an organic semi-conductor of p-type or n-type can be fabricated by introducing various substituents to the core structure having a property of n-type, thereby providing stability for the device.
- -
-
-
- Synthetic control of structural order in N-alkylthieno[3,4- c ]pyrrole-4,6-dione-based polymers for efficient solar cells
-
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.
-
supporting information; experimental part
p. 7595 - 7597
(2010/07/09)
-
- PYRROLINE DERIVATIVES AGAINST CELL RELEASING TUMOR NECROSIS FACTOR, PREPARATION METHODS AND USES THEREOF
-
Compounds represented by Formula (I) or Formula (II) against cell releasing TNFα, their pharmaceutically acceptable salts or hydrates and preparation methods and uses thereof, in which A and B represent CH2, CO, SO, or SO2; D represents S, NH, or NC1-6 alkyl; R1 represents H, or one or two same or different radical(s) selected from the group consisting of F, Cl, Br, C1-4 alkyl,OH,OC1-4 alkyl,NO2,NHC(O)C1-4 alkyl,NH2,NH(C1-4 alkyl), or N(C1-4 alkyl)2.
- -
-
Page/Page column 10
(2009/08/14)
-
- PYRROLINE-2-ONE DERIVATIVES AGAINST CELL RELEASING TUMOR NECROSIS FACTOR, PREPARATION METHODS AND USES THEREOF
-
Compounds represented by Formula (I) or Formula (II), their pharmaceutically acceptable salts or hydrates wherein A, B and E independently represent CH2 or CO; D represents S, NH, or NC1-6 alkylhydrocarbyl; R represents H or R3, R1 represents H, or 1-2 same or different occurrences of radical(s) selected from the group consisting of F, Cl, Br, C1-4 alkylhydrocarbyl, OH, OC1-4 alkylhydrocarbyl, NO2, NHC(O)C1-4 alkylhydrocarbyl, NH2, NH(C1-4 alkylhydrocarbyl), N(C1-4 alkylhydrocarbyl)2; and R2 represents F, CF3, H or C1-4 alkylhydrocarbyl; are active inhibitors of TNFα. Provided are also preparation methods and uses thereof.
- -
-
Page/Page column 12
(2009/09/07)
-
- DIOXYPYRROLO-HETEROAROMATIC COMPOUNDS AND ORGANIC ELECTRONIC DEVICES USING THE SAME
-
The present invention relates to dioxypyrrolo-heterocyclic compounds and an organic electronic device using the same. The compound of the present invention satisfies the requirements for use in an organic electronic device such as an organic light emitting device, an organic thin film transistor, and an organic solar cell, for example, suitable energy levels, and the electrochemical and thermal stability, by introducing various substituents to the core structure, and also have amorphous or crystalline property depending on the Mnd of the substituents, to satisfy the characteristics individually required for each of the devices. Further, an organic semi-conductor of p-type or n-type can be fabricated by introducing various substituents to the core structure having a property of n-type, thereby providing stability for the device.
- -
-
Page/Page column 15; 18-19
(2008/12/08)
-
- 5H-THIOENO(3,4-c)PYRROLE-4,6-DIONE DERIVATIVES AND THEIR USE AS TUMOR NECROSIS FACTOR INHIBITORS
-
Taught are derivatives of 5H-thioeno(3,4-c)pyrrole-4,6-dione, their organic, and inorganic salts, methods of synthesis of these derivatives, and their application as active pharmaceutical-ingredients useful as inhibitors of TNFα, the derivative being represented by the general formula (I): in which R1 represents H, C1-6alkyl, OR4, OC(O)R5, NO2, NHC(O)R6, or NR7R8; R2 represents H, a halogen, or C1-6alkyl; R3 represents H, methyl, isopropyl, allyl, benzyl, CH2CO2(C1-6alkyl), or CH2(CH2)nR9; R4, R5, R6, R7, and R8 each independently and at each occurrence represents H, or C1-6alkyl; R9 represents H, C1-6alkyl, OH, OC1-6alkyl, NH2, NHC1-6alkyl, N(C1-6alkyl)2, or CO2(C1-6alkyl); and n represents 1, 2, 3, or 4.
- -
-
Page/Page column 13
(2008/12/07)
-
- 5H-THIENO [3,4-c]PYRROLE-4, 6-DIONE DERIVATIVES AGAINST CELL RELEASING TUMOR NECROSIS FACTOR
-
Taught are derivatives of 5H-thieno (3,4-c) pyrrole-4,6-dione, their organic, and inorganic salts, methods of synthesis of these derivatives, and their application as active pharmaceutical-ingredients useful as inhibitors of TNFα, the derivative being represented by the general formula (I): in which R1 represents H, C1-6alkyl, OR4, OC(O)R5, NO2, NHC(O)R6, or NR7R8; R2 represents H, a halogen, or C1-6alkyl; R3 represents H, methyl, isopropyl, allyl, benzyl, CH2CO2 (C1-6alkyl), or CH2(CH2)nR9; R4, R5, R6, R7, and R8 each independently and at each occurrence represents H, or C1-6alkyl; R9 represents H, C1-6alkyl, OH, OC1-6alkyl, NH2, NHC1-6alkyl, N(C1-6alkyl)2, or CO2(C1-6alkyl); and n represents 1, 2, 3, or 4.
- -
-
Page/Page column 26-27
(2008/12/08)
-
- The preparation of 7-substituted norbornadiene-2,3-dicarboxylic anhydrides and an experimental and theoretical study of their reactivity
-
Four new substituted methano-bridged or heteroatom-bridged norbornadienomaleic anhydrides have been prepared and converted to sesquinorbornadiene anhydrides by reaction with cyclic 1,3-dienes. The versatility of parity reversal, in conjunction with N-substituent steric effects, has been used to produce all three possible stereoisomers of the N,O-sesquinorbornadiene anhydrides in separate, stereoselective cycloadditions. The anhydrides have been synthesized by cyclization of their diacids (in situ production) or by flash vacuum pyrolysis of their furan adducts (yielding crystalline products); further fragmentation occurs at these or higher temperatures to produce five-membered carbocyclic or heterocyclic anhydrides. Activation energies have been evaluated for the fragmentation and cycloaddition processes using DFT calculations (B3LYP/6-31G*) and these calculations correctly predict, which reaction can be intercepted at the norbornadienomaleic anhydride stage and preferred stereochemistry of cycloadducts.
- Margeti?, Davor,Warrener, Ronald N.,Sun, Guangxing,Butler, Douglas N.
-
p. 4338 - 4346
(2007/10/03)
-
- Biphenyl-4-ylcarbamoyl thiophene carboxylic acids as potent DHODH inhibitors
-
A previously discovered DHODH inhibitor series was further improved by replacing the cyclopentene ring by aromatic heterocycles. Different isomers of these compounds were prepared by the directed ortho-metallation procedure. The compounds are more active than the corresponding cyclopentene analogs and show potent effects on PBMC's proliferation.
- Leban, Johann,Kralik, Martin,Mies, Jan,Baumgartner, Roland,Gassen, Michael,Tasler, Stefan
-
p. 267 - 270
(2007/10/03)
-
- New regiosymmetrical dioxopyrrolo- and dihydropyrrolo-functionalized polythiophenes
-
(Chemical Equation Presented) We present the synthesis of two N-alkylated poly(dioxopyrrolothiophene)s and two N-alkylated poly(dihydropyrrolothiophene)s with potential application in the field of conducting polymers. The polymers are synthesized from the corresponding 2,5-dibromothiophenes by an Ullmann-type polymerization and a Stille-type polymerization, respectively. The two N-alkylated poly(dihydropyrrolothiophene)s are the first examples of amino-functionalized polythiophenes built from regiosymmetrical thiophene monomers.
- Nielsen, Christian B.,Bjornholm, Thomas
-
p. 3381 - 3384
(2007/10/03)
-
- Thermolysis of Thiophenedicarboxylic Acid Anhydrides as a Route to Five-Membered Hetarynes
-
Flow vacuum thermolysis (FVT) of the anhydrides of thiophene-2,3- (5) and -3,4-dicarboxylic acid (6) and of thianaphthene-2,3-dicarboxylic acid (7) in the presence of thiophene, 1,3-cyclohexadiene, or benzene gave thianthrene (15a), presumably by aromatization of an intermadiate Diels-Alder adduct of the diene traps and the aryne 2,3-didehydrothiophene (8).A similar rationale explains the formation of dibenzothiophene from 7 and thiophene, the four monomethylthianaphthenes 22-25 from 5 and cyclopentadiene, 5,6-dimethylthianaphthene (15f) from 5 and 2,3-dimethylbutadiene, and a mixture of hydroxythianaphthenes (15d) from 5 and furan.The latter reaction also produces a mixture of isomeric cyclopentanothiophenes (19) which probably arise by decarbonylation of 15d.An FVT reaction of 5 with propyne as the trap gave a mixture of allenyl-(28) and propynylthiophenes 29 which probably arise by an ene reaction of the trap and the aryne 8.Decomposition of the anhydrides 5 and 6 in molten anthracene led only to Friedel-Crafts products such as thienylanthracenes 33 and quinones 34 from 5 and 39 and 40 from 6.The diene reactivity of thiophene 13a in the gas phase was demonstrated by the formation of naphthalene from its reaction with benzyne generated from the thermolysis of indanetrione and by the formation of indene from 13a plus cyclopentadiene.Possible, but improbable, interpretations of the FVT results without invoking a five-membered hetaryne intermediate are considered.
- Reinecke, Manfred G.,Newsom, James G.,Chen, Lao-Jer
-
p. 2760 - 2769
(2007/10/02)
-