cas 125143-53-5, 3,3',5,5'-Tetrabromo-2,2'-bithiophene

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Synthesis, characterization, and transistor response of semiconducting silole polymers with substantial hole mobility and air stability. Experiment and theory
Realizing p-channel semiconducting polymers with good hole mobility, solution processibility, and air stability is an important step forward in the chemical manipulation of charge transport in polymeric solids and in the development of low-cost printed electronics. We report here the synthesis and full characterization of the dithienosilole- and dibenzosilole-based homopolymers, poly(4,4-di-n-hexyldithienosilole) (TS6) and poly(9,9-di-n- octyldibenzosilole) (BS8), and their mono- and bithiophene copolymers, poly(4,4-di-n-hexyldithienosilole-alt-(bi)thiophene) (TS6T1, TS6T2) and poly(9,9-di-n-octyldibenzosilole-alt-(bi)thiophene) (BS8T1,BS8T2), and examine in detail the consequences of introducing dithienosilole and dibenzosilole cores into a thiophene polymer backbone. We demonstrate air-stable thin-film transistors (TFTs) fabricated under ambient conditions having hole mobilities as large as 0.08 cm2/V·s, low turn-on voltages, and current on/off ratios > 106. Additionally, unencapsulated TFTs fabricated under ambient conditions are air-stable, an important advance over regioregular poly(3-hexylthiophene) (P3HT)-based devices. Density functional theory calculations provide detailed insight into the polymer physicochemical and charge transport characteristics. A direct correlation between the hole injection barrier and both TFT turn-on voltage and TFT polymer hole mobility is identified and discussed, in combination with thin-film morphological characteristics, to explain the observed OTFT performance trends.
Lu, Gang,Usta, Hakan,Risko, Chad,Wang, Lian,Facchetti, Antonio,Ratner, Mark A.,Marks, Tobin J.
p. 7670 - 7685
(2008)
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Novel blue-light-emitting hybrid materials based on oligothiophene acids and ZnO
Novel blue-light-emitting materials based on ZnO and 2,2′-bithiophene-5,5′-dicarboxylic acid (DTDA), 4′,3″-dipentyl-5,2′: 5′,2″: 5″,2?-quaterthiophene-2,5?-dicarboxylic acid (QTDA) have been prepared. The hybrid materials show that the PL λmax are at 450 and 425 nm for DTDA-ZnO and QTDA-ZnO, respectively.
Jiu, Tonggang,Liu, Huibiao,Fu, Liming,He, Xiaorong,Wang, Ning,Li, Yuliang,Ai, Xicheng,Zhu, Daoben
p. 113 - 117
(2004)
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Very large silacylic substituent effects on response in silole-based polymer transistors
Understanding the interrelationships between molecular structure and organic thin film transistor performance is key to the realization of novel organic semiconductors achieving superior device characteristics. Herein we report the synthesis, characterization, and charge-transporting properties in organic field-effect transistors (OFETs) of dithieno silole-based oligomers and copolymers having silacycloalkyl substituents. Silacyclization of the alkyl substituents on the silole silicon atom reduces steric encumbrance, contracts solid state intermolecular π-π contacts, and enhances the charge-transport capacity of the oligomers. Oligomer 3,3′-dihexylsilylene-2,2′:5, 2′′:5′,2′′′:5′′, 2′′′′:5′′′,2′′′ ′′-sexithiophene (SM5) with two Si-n-hexyl substituents is not FET-active, while the mobilities of 3,3′-cyclopentanylsilylene-2,2′: 5,2′′:5′,2′′′:5′′, 2′′′′:5′′′,2′′′ ′′′-sexithiophene (SM4) and 3,3′-cyclobutysilylene-2, 2′:5,2′′:5′,2′′′:5′′, 2′′′′:5′′′,2′′′ ′′-sexithiophene (SM3) FETs are 2.6 × 10-4 and 3.4 × 10-4 cm2/(V s), respectively. Single crystal structural data and melting point derived intermolecular packing trends parallel these FET results. Copolymers P1-P4 based on the same dithienosilole cycloalkyl cores exhibit optimized hole mobilities of 2 × 10-5, 6 × 10-4, 3 × 10-4, and 2 × 10-3 cm2/V?s, respectively, lower than that of analogous silole-containing polymers with long Si-alkyl substituents, implying that the solubilizing and self-assembly functions of Si-alkyl substituents are important for optimizing the mobility. Interestingly, copolymer [poly{[N,N′-bis(2- octyl-dodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5′-(3, 3′-cyclopentanylsilylene-2,2′-bithiophene (P5) films are the most ordered and exhibit a good electron mobility of 4 × 10-3 cm2/V?s after thermal annealing. All of these OFETs exhibit good ambient-stability, which is attributed to their low-lying HOMOs (>0.2 eV lower than that of P3HT), a consequence of introducing silole cores into polythiophene backbones.
Huang, Hui,Youn, Jangdae,Ponce Ortiz, Rocio,Zheng, Yan,Facchetti, Antonio,Marks, Tobin
p. 2185 - 2200
(2011)
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Terpyridine-based donor-acceptor metallo-supramolecular polymers with tunable band gaps: Synthesis and characterization
Three new building blocks containing the electron-donor fused-ring motifs carbazole, dithienosilole (DTS) and dithienopyrrole (DTP) and the 2,2′:6′,2″-terpyridine electron-acceptor motif were designed and synthesized. Directed by transition metal ions, the self-assembly of the building blocks triggered polymerization to form the corresponding metallo-supramolecular polymers PCzTPY, PSiTPY and PNTPY, respectively. The UV-vis absorption maxima of the building blocks occur at long wavelengths (351, 368 and 430 nm for CzTPY, SiTPY and NTPY, respectively), which arises from intramolecular charge transfer (ICT) transitions. However, the absorption maxima of their corresponding metallo-supramolecular polymers are clearly red-shifted (to 394, 431 and 509 nm for PCzTPY, PSiTPY and PNTPY, respectively), which is caused by the incorporation of the transition metal ion into the backbones of the target polymers. Based on the above strategies, the resulting metallo-polymers exhibit reduced energy gaps, which are 2.07, 1.97 and 1.56 eV for the PCzTPY, PSiTPY and PNTPY metallo-supramolecular polymers, respectively.
Li, Fanchao,Hu, Zhiwei,Qiao, Hongbing,Liu, Lin,Hu, Jiawei,Chen, Xuegang,Li, Jie
p. 142 - 150
(2016)
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Synthesis and characterization of conjugated low band-gap terpolymers incorporating carbazole for photovoltaic application
A series of photoactive conjugated low band-gap copolymer (CPSB) and terpolyemrs (TPSBCz-n, n = 1 to 4) based on N-alkyl carbazole, 4,4'-dialkyl dithienosilole, and bezothiadiazole were synthesized. The copolymer and terpolymers were built with the fraction of the carbazole unit varied for 0, 2.5, 5, 10 and 25 mol%. Among the mixtures, the composition of 25 wt% of terpolymer bearing 10 mol.% of the carbazole unit, TPSBCz-3, and 75 wt% of C71-PCBM found a power conversion efficiency of 0.86% with a open-circuit voltage of 0.59 V, the short-circuit current of 4.85 mA and fill factor of 0.30 under AM 1.5 spectral illumination. Our findings suggest that terpolymer bearing low concentration of carbazole lead to a high power conversion efficiency with improved the short-circuit current due to hole mobility enhancement effect of carbazole unit. Copyright
Kim, Ki-Won,Na, Hyungjun,So, Won-Wook,Yoon, Sung Cheol,Shin, Won Suk
p. 4279 - 4283
(2012)
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Halogenation Using Quaternary Ammonium Polyhalides. XXXI. Halogenation of Thiophene Derivatives with Benzyltrimethylammonium Polyhalides
The reactions of thiophene derivatives with benzyltrimethylammonium tetrachloroiodate, benzyltrimethylammonium tribromide, and benzyltrimethylammonium dichloroiodate in acetic acid or in acetic acid-zinc chloride under mild conditions gave chloro-, bromo-, and iodo-substituted thiophene derivatives, respectively, in satifactory yields.
Okamoto, Tsuyoshi,Kakinami, Takaaki,Fujimoto, Hiroshi,Kajigaeshi, Shoji
p. 2566 - 2568
(1991)
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Designing conducting polymer-based sensors: selective ionochromic response in Crown Ether containing polythiophenes
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Marsella, Michael J.,Swager, Timothy M.
p. 12214 - 12215
(1993)
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Hemilabile Ligands as Mechanosensitive Electrode Contacts for Molecular Electronics
Single-molecule junctions that are sensitive to compression or elongation are an emerging class of nanoelectromechanical systems (NEMS). Although the molecule–electrode interface can be engineered to impart such functionality, most studies to date rely on poorly defined interactions. We focused on this issue by synthesizing molecular wires designed to have chemically defined hemilabile contacts based on (methylthio)thiophene moieties. We measured their conductance as a function of junction size and observed conductance changes of up to two orders of magnitude as junctions were compressed and stretched. Localised interactions between weakly coordinating thienyl sulfurs and the electrodes are responsible for the observed effect and allow reversible monodentate?bidentate contact transitions as the junction is modulated in size. We observed an up to ≈100-fold sensitivity boost of the (methylthio)thiophene-terminated molecular wire compared with its non-hemilabile (methylthio)benzene counterpart and demonstrate a previously unexplored application of hemilabile ligands to molecular electronics.
Algethami, Norah,Ferri, Nicolò,Higgins, Simon J.,Lambert, Colin J.,McLaughlin, Maeve,Nichols, Richard J.,Sadeghi, Hatef,Sangtarash, Sara,Vezzoli, Andrea
p. 16583 - 16589
(2019)
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Preparation and properties of thienyl and 2,2'-substituted cobalt-bis(semiquinone) tautomers
The synthesis and characterization of two new 2,2'-bipyridine ligands containing 3-ethynylthiophene and 3,3'-diethynyl-2,2'-bithiophene substituents is presented, along with the preparation, electronic, and magnetic properties of monoand bimetallic cobalt-semiquinone valence tautomers containing these ligands.
O'Sullivan, Thomas J.,Djukic, Brandon,Dube, Paul A.,Lemaire, Martin T.
p. 533 - 538
(2009)
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Pd-Catalyzed Aerobic Oxidative Coupling of Thiophenes: Synergistic Benefits of Phenanthroline Dione and a Cu Cocatalyst
Substituted bithiophenes are prominent fragments in functional organic materials, and they are ideally prepared via direct oxidative C-H/C-H coupling. Here, we report a novel PdII catalyst system, employing 1,10-phenanthroline-5,6-dione (phd) as the ancillary ligand, that enables aerobic oxidative homocoupling of 2-bromothiophenes and other related heterocycles. These observations represent the first use of phd to support Pd-catalyzed aerobic oxidation. The reaction also benefits from a Cu(OAc)2 cocatalyst, and mechanistic studies show that Cu promotes C-C coupling, implicating a role for CuII different from its conventional contribution to reoxidation of the Pd catalyst.
Tereniak, Stephen J.,Bruns, David L.,Stahl, Shannon S.
p. 20318 - 20323
(2020)
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Selective halogenation of bithiophenes using 2-halopyridazin-3(2H)-ones under ambient conditions
2,2′-Bithiophene and halogenated-2,2′-bithiophenes were halogenated with 2-halo-4,5-dichloropyridazin-3(2H)-one in the presence of zinc halide to give selectively the corresponding dihalo-, trihalo-, and tetrahalo-2,2′-bithiophenes involving the same or different halogens in excellent yields, respectively. Georg Thieme Verlag Stuttgart.
Jung, Kwang-Ju,Seung, Beom Kang,Won, Ju-Eun,Park, Song-Eun,Ki, Hun Park,Jong, Keun Park,Lee, Sang-Gyeong,Yoon, Yong-Jin
p. 490 - 494
(2009)
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SELECTIVE FUNCTIONALIZATION OF 2,2'-BITHIOPHENES
The selective functionalization of the 2,2'-bithiophene molecule is described.Selective alkyl substitution at the 3,3'-positions was achieved by sequential bromination of the 3,3' and 5,5' positions followed by debromination at the 5,5'-positions.The resultant 3,3'-dibromo-2,2'-bithiophene was transformed via a Grignard reaction to give a series of 3,3'-dialkyl-2,2'-bithiophenes.Finally, nitration of the active 5,5'positions gave the corresponding 3,3'-dialkyl-5,5'-dinitro-2,2'-bithiophenes.
Khor, Eugene,Ng, Siu Choon,Li, Hwee, Chze,Chai, Selenium
p. 1805 - 1812
(1991)
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Dithienosilole- and dibenzosilole-thiophene copolymers as semiconductors for organic thin-film transistors
The synthesis and physicochemical properties of a new class of thiophene/arenesilole-containing π-conjugated polymers are reported. Examples of this new polymer class include the following: poly(2,5-bis(3′,3′′-dihexylsilylene-2′,2′′-bithieno)thiophene) (TS6T1), poly(2,5′-bis(3′′,3′″-dihexylsilylene-2′′,2′″-bithieno)bithiophene) (TS6T2), poly(2,5′-bis(2′′,2′″-dioctylsilylene-1′′,1′″-biphenyl)thiophene) (BS8T1), and poly(2,5′-bis(2′′,2′″-dioctylsilylene-1′′,1′″-biphenyl)bithiophene) (BS8T2). Organic field-effect transistors (OFETs) with hole carrier mobilities as high as 0.02-0.06 cm2/V s in air, low turn-on voltages, and current on/off ratios >105-106 are fabricated using solution processing techniques with the above polymers as the active channel layer. OFETs based on this polymer class exhibit excellent ambient operational stability. Copyright
Usta, Hakan,Lu, Gang,Facchetti, Antonio,Marks, Tobin J.
p. 9034 - 9035
(2006)
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Iridium(iii) complexes with the dithieno[3,2-: B:2′,3′- d] phosphole oxide group and their high optical power limiting performances
A new 2-phenylpyridine-type (ppy-type) ligand with the dithieno[3,2-b:2′,3′-d]phosphole oxide (DTPO) group has been successfully synthesized. Based on this novel ligand, three cyclometalated iridium(iii) complexes (P-Ir-P, P-Ir-T and P-Ir-C) are synthesized with symmetrical and unsymmetrical structures. Photophysical results reveal that these cyclometalated iridium(iii) complexes can show weak near-infrared (NIR) phosphorescence emission with wavelengths of 739 nm for P-Ir-P, 750 nm for P-Ir-T and 746 nm for P-Ir-C. Importantly, transient absorption characterization shows that these cyclometalated iridium(iii) complexes can exhibit strong excited state absorption in the range of ca. 520 to 700 nm, indicating their optical power limiting (OPL) potential in this wavelength range. Open-aperture Z-scan against a 532 nm laser shows their OPL ability in the order of P-Ir-P > P-Ir-C > P-Ir-T. Complex P-Ir-P shows an even better OPL ability than the state-of-the-art OPL material C60, indicating the important potential application of these cyclometalated iridium(iii) complexes as new OPL materials.
Li, Ming,Liu, Zhao,Sun, Yuanhui,Xu, Yanmin,Yan, Lihe,Yang, Xiaolong,Yue, Ling,Zhou, Guijiang
supporting information
p. 4967 - 4976
(2020/04/24)

Dialkylthienosilole and N-alkyldithienopyrrole-based copolymers: Synthesis, characterization, and photophysical study
We synthesized and characterized a set of D-π-A conjugated copolymers containing thiophene π-bridge. While benzothiadiazole serves as an acceptor (A) unit, the 4,4-dialkyldithieno[3,2-b:2′,3′-d]silole (DTSi) or N-alkyldithieno[3,2-b:2′,3′-d]pyrrole (DTP) act as a donor (D) unit. The copolymers were synthesized via the commonly Stille cross-coupling reaction and exhibited molecular weights of 18.6 to 31.3 kg/mol. The main structural differences among the copolymers are the type of donor moiety (DTSi or DTP) and the position of hexyl side chains on the thiophene π-bridge units between the D and A moieties. The ultimate goal of this work is to explore the effect of three structural factors that could control the photophysical properties of polymers in order to help in the rational design of polymers having specific properties used in optoelectronic devices. The physical properties include thermal stability, photophysical, and electrochemical properties. The structural factors are (a) the power of donor moiety, (b) the position of alkyl side chain on the thiophene π-bridge, and (c) the nature of the alkyl side chain. Also, we utilized the density functional theory calculations to calculate the geometric and electronic structures. A good agreement was remarked between the experimental and theoretical findings.
El-Shehawy, Ashraf A.,Abdo, Nabiha I.,El-Hendawy, Morad M.,Abdallah, Abdul-Rahman I.A.,Lee, Jae-Suk
(2020/03/04)

Method for Aerobic Oxidative Coupling of Thiophenes with a Ligand-Supported Palladium Catalyst
An oxidative homocoupling method of synthesizing certain 2,2′-bithiophenes from thiophenes using oxygen as the terminal oxidant is disclosed. In non-limiting examples, the method uses oxygen along with a catalytic system that includes palladium, an assistive ligand, and a non-palladium metal additive to catalyze one of the following reactions: Associated catalytic systems and compositions are also disclosed.
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Paragraph 0095

(2019/07/23)

Preparation method of thiophene organic semiconductor material intermediate
The invention relates to a preparation method of a thiophene organic semiconductor material intermediate, which comprises the following steps: (1) reacting 2,2'-bithiophene with a halogenating agent to obtain tetrahalogen-substituted bithiophene; (2) selectively removing halogen at the ortho-position of tetrahalogen-substituted bithiophene to obtain meta-dihalogen-substituted bithiophene; and (3)under the protection of an inert atmosphere and in the presence of a catalyst, reacting the meta-dihalogen-substituted bithiophene with dichloro(2-ethylhexyl)octylsilane to synthesize the target product 4-(2-ethylhexyl)-4-octyl-4-silyl[3,2-b:4,5-b']dithiophene. The preparation method of the thiophene organic semiconductor material intermediate is simple in process, substances with severe corrosivity or toxicity are not used, the intermediate 3,3'-dibromo-2,2'-bithiophene does not need further reaction treatment, and the intermediate 3,3'-dibromo-2,2'-bithiophene can react with the dichloro(2-ethylhexyl)octylsilane to synthesize the target product.
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Paragraph 0036; 0038-0045

(2020/01/08)

Cross-shaped small organic molecule hole transport material and preparation method
The invention provides a cross-shaped small organic molecule hole transport material and a preparation method. The preparation method comprises the following steps: uniformly mixing 5-hexyl-5'-trimethyl-2,2'-bithiophene or 5-octyl-5'-trimethyl-2,2'-bithiophene with 3,3',5,5'-tetrabromo-2,2'-bithiophene in methylbenzene at a molar ratio of 1:(4-6); performing a reaction at the temperature of 90-120DEG C for 18-25h, cooling to room temperature and adding silica gel powder for spin drying; separating and purifying a coarse product after spin drying with dichloromethane and n-hexane at a ratio of1:(5-20) as an eluting agent to obtain the cross-shaped small organic molecule hole transport material which is shown in the structural formula I as shown in the specification or the structural formula II as shown in the specification. Due to the 'x' rotary cross-shaped structure of the hole transport material, the excessive crystallization can be effectively inhibited, so that a thiophene derivative have good solubility and excellent hole transport performance under the condition that no excessive alkyl substituted units are introduced; the current density and the photoelectric conversion efficiency of a device can be greatly improved after the cross-shaped small organic molecule hole transport material is applied in an all-inorganic perovskite solar cell.
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Paragraph 0020-0022; 0031-0032; 0039-0041; 0050-0051

(2019/07/04)

[...] compounds (by machine translation)
[Problem] self-assembly to form an integrated spiral, circular polarized light emitting [...] shown compound. (1) a compound represented by the formula [a] [...]. (R1 And R2 Both or either one of the substrate having asymmetric centers; R4 OR is hydrogen or3 )Figure 1 [drawing] (by machine translation)
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Paragraph 0024; 0028-0029

(2017/11/18)

FUSED RING DERIVATIVE AND ORGANIC SOLAR CELL COMPRISING THE SAME
The present invention relates to a condensed cyclic derivative represented by chemical formula 1, and an organic solar cell containing the same. According to an embodiment of the present invention, the condensed cyclic derivative exhibits excellent coating properties by having a hydroxyl group, an alkyl group, an alkoxy group, and a sulfide group as a substituent.COPYRIGHT KIPO 2017
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(2017/08/02)

Synthesis and photophysical properties of semiconductor molecules D1-A-D2-A-D1-type structure based on derivatives of quinoxaline and dithienosilole for organics solar cells
A novel small molecule with D1-A-D2-A-D1 structure denoted as DTS(QxHT2)2 based on quinoxaline acceptor and dithienosilone donor units was synthesized and its optical and electrochemical properties were investigated. The thin film of DTS(QxHT2)2 showed a broad absorption profile covering the solar spectrum from 350?nm to 780?nm with an optical bandgap of 1.63?eV. The energy levels estimated from the cyclic voltammetry indicate that this small molecule is suitable as donor along with PC71BM as acceptor for the fabrication solution processed bulk heterojunction solar cells for efficient exciton dissociation and high open circuit voltage. The organic solar cells based on optimized DTS(QxHT2)2:PC71BM active layers processed with chloroform and DIO/CF showed overall power conversion efficiency of 3.16% and 6.30%, respectively. The higher power conversion efficiency of the solar cell based on the DIO/CF processed active layer is attributed to enhanced short circuit photocurrent and fill factor may be related to better phase separation between donor and acceptor in the active layer and more balanced charge transport, induced by the solvent additive. The power conversion efficiency of the organic solar cell was further improved up to 7.81% based on active layer processed with solvent additive, using CuSCN as hole transport layer instead of PEDOT:PSS and mainly attributed to increased fill factor and open circuit voltage due the formation of better Ohmic contact between the active layer and the CuSCN layer.
Keshtov,Godovsky, D. Yu,Kuklin,Nicolaev,Lee,Lim,Lee,Koukaras,Sharma, Ganesh D.
p. 361 - 370
(2016/11/09)

organic semiconductor compound, manufacturing method thereof, and organic electronic device that contains it
The present invention relates to an organic semiconductor compound, a method for manufacturing the same, and an organic electronic device comprising the same and, more specifically, to an organic semiconductor compound including quinoxaline, a method for manufacturing the same, and an organic electronic device comprising the same. In addition, by having a low band gap by synthesizing and copolymerizing a thiophene derivative containing sulfur (S) with a quinoxaline-based compound, the organic electronic device comprising the same has a higher efficiency with an innovative combination with a fullerene derivative, which is a photoactive layer, with the organic semiconductor compound of the present invention. The organic semiconductor compound of the present invention has high thermal stability and high solubility and the organic electronic device comprising the same has excellent electric characteristics, thereby can be valuably used as a n-type material of the organic electronic device, especially an organic solar cell or an organic thin film transistor.
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Paragraph 0200-0203

(2016/10/09)

Low bandgap dicyanovinyl and tricyanovinyl oligothiophenes for solar cell applications
The invention relates to solution-processable, p-type, low-optical gap oligothiophene compounds for use in solar cell application, comprising at least one thiophene-containing group, at least one electron-withdrawing dicyanovinyl or tricyanovinyl group, and at least one electron-donating diphenylaminofluorenyl or N-alkylcarbazole group.
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Page/Page column 10; 11; 12; 17

(2015/03/16)

Condensed compound and organic light emitting diode comprising the same
Provided are a condensed cyclic compound represented by chemical formula 1 and an organic electroluminescent device comprising the same. In the chemical formula 1, X, and R1 to R10 refer to the detailed description of the present invention. An organic light emitting device having an organic layer comprising the condensed cyclic compound has properties of low driving voltage, high light emitting efficiency and long lifespan.COPYRIGHT KIPO 2016
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(2016/12/01)

The effect of heteroatom conformation on optoelectronic properties of cyclopentadithiophene derivatives
Cyclopentadithiophene (CPDT) derivatives with different heteroatom conformations have been synthesized. The optical, electrochemical and charge transport properties of these molecules are reported. The CPDT-anti-ketone not only exhibits the lowest optical and electronic bandgaps, but also exhibits reasonable hole mobility, 3 × 10-3 cm2 (V s) -1. Changing the carbonyl conformation to the syn position or incorporating the imine functionality results in a blue-shift in the lower energy band of the absorption spectrum indicative of the increased bandgaps. the Partner Organisations 2014.
Wanwong, Sompit,Poe, Ambata,Balaji, Ganapathy,Thayumanavan
supporting information
p. 2474 - 2478
(2014/04/03)

Synthesis and photovoltaic applications of a 4,4′- spirobi[cyclopenta[2,1-b;3,4-b′]dithiophene]-bridged donor/acceptor dye
A new donor/acceptor (D-A) spiro dye (SCPDT1) featuring two bithiophene units, connected through an sp3-hybridized carbon atom, was prepared by a multistep synthetic sequence involving the convenient assembly of the spiro system under mild catalytic conditions. The photocurrent spectrum of dye-sensitized solar cells incorporating SCPDT1 covers the spectral region ranging from 350 to 700 nm and reaches a wide maximum of ～80% in the 420-560 nm range. Power conversion efficiencies of up to 6.02% were obtained.
Pozzi, Gianluca,Orlandi, Simonetta,Cavazzini, Marco,Minudri, Daniela,Macor, Lorena,Otero, Luis,Fungo, Fernando
supporting information
p. 4642 - 4645
(2013/10/08)

Synthetic principles directing charge transport in low-band-gap dithienosilole-benzothiadiazole copolymers
Given the fundamental differences in carrier generation and device operation in organic thin-film transistors (OTFTs) and organic photovoltaic (OPV) devices, the material design principles to apply may be expected to differ. In this respect, designing organic semiconductors that perform effectively in multiple device configurations remains a challenge. Following "donor-acceptor" principles, we designed and synthesized an analogous series of solution-processable π-conjugated polymers that combine the electron-rich dithienosilole (DTS) moiety, unsubstituted thiophene spacers, and the electron-deficient core 2,1,3-benzothiadiazole (BTD). Insights into backbone geometry and wave function delocalization as a function of molecular structure are provided by density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) level. Using a combination of X-ray techniques (2D-WAXS and XRD) supported by solid-state NMR (SS-NMR) and atomic force microscopy (AFM), we demonstrate fundamental correlations between the polymer repeat-unit structure, molecular weight distribution, nature of the solubilizing side-chains appended to the backbones, and extent of structural order attainable in p-channel OTFTs. In particular, it is shown that the degree of microstructural order achievable in the self-assembled organic semiconductors increases largely with (i) increasing molecular weight and (ii) appropriate solubilizing-group substitution. The corresponding field-effect hole mobilities are enhanced by several orders of magnitude, reaching up to 0.1 cm2 V-1 s-1 with the highest molecular weight fraction of the branched alkyl-substituted polymer derivative in this series. This trend is reflected in conventional bulk-heterojunction OPV devices using PC71BM, whereby the active layers exhibit space-charge-limited (SCL) hole mobilities approaching 10-3 cm2 V-1 s-1, and yield improved power conversion efficiencies on the order of 4.6% under AM1.5G solar illumination. Beyond structure-performance correlations, we observe a large dependence of the ionization potentials of the polymers estimated by electrochemical methods on polymer packing, and expect that these empirical results may have important consequences on future material study and device applications.
Beaujuge, Pierre M.,Tsao, Hoi Nok,Hansen, Michael Ryan,Amb, Chad M.,Risko, Chad,Subbiah, Jegadesan,Choudhury, Kaushik Roy,Mavrinskiy, Alexei,Pisula, Wojciech,Bredas, Jean-Luc,So, Franky,Muellen, Klaus,Reynolds, John R.
supporting information; experimental part
p. 8944 - 8957
(2012/07/02)

Efficient synthesis of benzo[1,2- b:6,5- b']dithiophene-4,5-dione (BDTD) and its chemical transformations into precursors for π-conjugated materials
A straightforward synthesis of the fused-aromatic dione benzo[1,2-b:6,5-b']dithiophene-4,5-dione (BDTD) has been developed. This fused-aromatic dione was subjected to various chemical transformations to generate diverse molecules with potential use in π-conjugated materials for organic electronics.
Arroyave, Frank A.,Richard, Coralie A.,Reynolds, John R.
supporting information
p. 6138 - 6141
(2013/02/23)

Supramolecular functionalization of single-walled carbon nanotubes (SWNTs) with dithieno[3,2- b:2′,3′-d ]pyrrole (DTP) containing conjugated polymers
Fluorene and dithieno[3,2-b:2′,3′-d]pyrrole (DTP) containing conjugated polymers, {2,7-[9,9-didodecylfluorene]-alt-2,6-[N-dodecyldithieno(3, 2-b:2′,3′-d)pyrrole]} (PF-DTP1) and {2,7-[9,9-didodecylfluorene]- alt-2,6-[N-3,4,5(n-dodecyloxy)phenyldithieno(3,2-b:2′,3′-d)pyrrole]} (PF-DTP2), have been successfully synthesized using Suzuki polycondensation. These polymers possess excellent thermal stability with decomposition temperatures over 365 °C under Ar. The introduction of soluble side chains on the DTP units and incorporation with soluble dialkyl-substituted fluorene resulted in highly soluble polymers with novel optoelectronic properties. The supramolecular complex formation of these DTP containing polymers with single-walled carbon nanotubes (SWNTs) has been studied, and it was found that these polymers can form strong supramolecular polymer-nanotube assemblies and produce stable complexes in solution. UV-vis-NIR absorption, photoluminescence excitation (PLE), and Raman spectroscopy were used for the characterization and identification of the nanotube species that are present in THF solution. The strong nanotube emission was observed from individual SWNTs even after removal of excess free polymer by filtration and washing. On the basis of these two polymers, it was found that the interactions with the SWNT surface are more strongly dictated by the polymer backbone than the side chain, though further studies may be warranted.
Imin, Patigul,Imit, Mokhtar,Adronov, Alex
scheme or table
p. 9138 - 9145
(2012/04/18)

Synthesis and characterization of bridged bithiophene-based conjugated polymers for photovoltaic applications: Acceptor strength and ternary blends
Six of three-component donor-acceptor random copolymers P1-P6, symbolized as (thiophene donor)m -(thiophene acceptor)n, were rationally designed and successfully synthesized by the palladium-catalyzed Stille coupling. The 4H-cyclopenta[2,l-b:3,4-b']dithiophene (CPDT) unit serves as the donor for Pl-P4, while the benzothiadiazole (BT), quinoxaline (QU), dithienoquinoxaline, and thienopyrazine (TP) units are used as the acceptor for P1, P2, P3, and P4, respectively. P5 and P6 are structurally analogous to P1 and P2 except for using the dithieno[3,2-b:2',3'-d]silole (DTS) unit as the donor. Because the band gap lowering ability of the acceptor units in the polymer is in the order TP > BT > QU presumably due to the quinoid form population in the polymers, the optical band gaps can be well adjusted to be 1.2,1.6, and 1.8 eV for P4, P1, and P2, respectively. It is found that the two bridged bithiophene units, CPDT and DTS, have similar steric and electronic effects on the P1 and P5 as well as P2 and P6, respectively, leading to comparable intrinsic properties and device performances. Bulk heterojunction photovoltaic cells based on ITO/PEDOT:PSS/polymer:PC7BM/Ca/Al configuration were fabricated and characterized. Although P4 exhibits the lowest optical band gap, broadest absorption spectrum, and highest mobility, the too low-lying LUMO level hinders the efficient exciton dissociation, resulting in a low PCE of 0.7%. Compared with poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b'] dithiophene)-alt-4,7-(2,l,3-benzothiadiazole)] (PCPDTBT), random copolymer P1 shows more blue-shifted, broader absorption spectrum, comparable mobility, and a higher PCE of 2.0%. In view of the fact that P1 shows a higher band gap with strong absorption in visible region, while PCPDTBT has a lower band gap to mainly absorb NIR light, a BHJ device with the active layer containing ternary blend of PCPDTBT/P1/PC71BM was investigated and achieved an enhanced PCE of 2.5%, which outperforms the devices based on the binary blending systems of PCPDTBT/ PC71BM(PCE = 1.4%)orP1/PC71BM(PCE = 2.0%) under the identical conditions. Such an improvement is ascribed to the complementary absorption and compatible structure of P1 and PCPDTBT polymers.
Chen, Chiu-Hsiang,Hsieh, Chao-Hsiang,Dubosc, Martin,Cheng, Yen-Ju,Hsu, Chain-Shu
experimental part
p. 697 - 708
(2011/10/08)

POLYHETEROCYCLIC COMPOUND, ORGANIC ELECTRONIC DEVICE USING POLYHETEROCYCLIC COMPOUND, AND ELECTRONIC APPARATUS INCLUDING ORGANIC ELECTRONIC DEVICE
Disclosed is a novel polyheterocyclic compound, an organic electronic device using the polyheterocyclic compound, and an electronic apparatus including the organic electronic device. The polyheterocyclic compound has excellent solubility to solvent and high charge mobility. The organic electronic device produced by using the polyheterocyclic compound has excellent performance and is easily produced.
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Page/Page column 13-15

(2010/10/03)

Phenacyl-thiophene and quinone semiconductors designed for solution processability and air-Stability in high mobility n-channel field-effect transistors www.chemeurj.org
Electron-transporting organic semiconductors (n-channel) for fieldeffect transistors (FETs) that are processable in common organic solvents or exhibit air-stable operation are rare. This investigation addresses both these challenges through rational molecular design and computational predictions of n-channel (FETs) air-stability. A series of seven phenacyl-thiophene-based materials are reported incorporating systematic variations in molecular structure and reduction potential. These compounds are as follows: 5,5?-bis(perfluorophenylcarbonyl)-2,2′:5′,-2″:5″, 2?-quaterthiophene (1), 5,5?-bis-(phenacyl)-2,2′;5′, 2″: 5″,2?-quaterthiophene (2), poly[5,5?- (perfluorophenac-2-yl)-4′,4″-dioctyl-2,2':5',2":5", 2'"-quaterthiophene) (3), 5,5?-bis(perfluorophenacyl)-4,4?- dioctyl-2,2′:5′,2″:5″,2?-quaterthiophene (4), 2,7-bis((5-perfluorophenacyl)thiophen-2-yl)-9,10phenanthrenequinone (5), 2,7-bis[(5phenacyl)thiophen-2-yl]-9,10-phenanthrenequinone (6), and 2,7-bis(thiophen-2-yl)-9,10-phenanthrenequinone, (7). Optical and electrochemical data reveal that phenacyl functionalization significantly depresses the LUMO energies, and introduction of the quinone fragment results in even greater LUMO stabilization. FET measurements reveal that the films of materials 1, 3, 5, and 6 exhibit n-channel activity. Notably, oligomer 1 exhibits one of the highest, μe (up to ≈0.3 Cm 2V-1S-1) values reported to date for a solutioncast organic semiconductor; one of the first n-channel polymers, 3, exhibits μe ≈ 10-6 Cm2V -1S-1 in spin-cast films (μc = 0.02 cm 2 V-1S-1 for drop-cast 1:3 blend films); and rare air-stable n-channel material 5 exhibits n-channel FET operation with μe = 0.015 cm2V-1s-1, while maintaining a large Ion:off= 106 for a period greater than one year in air. The crystal structures of 1 and 2 reveal close herringbone interplanar π-stacking distances (3.50 and 3.43 A, respectively), whereas the structure of the model quinone compound, 7, exhibits 3.48 A cofacial π-stacking in a slipped, donor-acceptor motif.
Letizia, Joseph A.,Cronin, Scott,Ortiz, Rocio Ponce,Facchetti, Antonio,Ratner, Mark A.,Marks, Tobin J.
experimental part
p. 1911 - 1928
(2010/06/16)

Palladium-catalyzed cross-coupling reactions of dithienosilole with indium reagents: Synthesis and characterization of dithienosilole derivatives and their application to organic light-emitting diodes
Three dithienosilole (DTS) derivatives bearing naphthyl segments, 5,5′-dinaphthyl-1,1-dimethyldithienosilol (1), 5,5′-dinaphthyl-1- methyl-1-phenyldithienosilole (2), and 5,5′-dinaphthyl-1,1- diphenyldithienosilol (3), are prepared through Pd(II)-catalyze
Jung, Hwasoon,Hwang, Hyonseok,Park, Ki-Min,Kim, Jinho,Kim, Dong-Ha,Kang, Youngjin
scheme or table
p. 2715 - 2723
(2010/08/06)

NONLINEAR OPTICAL MATERIAL COMPOSITION AND METHOD OF MANUFACTURE
Embodiments of the present disclosure provide non-linear optical compounds and compositions comprising a silole-derivative. In an embodiment, the silole derivative comprises a chromophore including a structure represented by Formula (A): wherein each Of R
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Page/Page column 25-26

(2008/12/08)

n-channel polymers by design: Optimizing the interplay of solubilizing substituents, crystal packing, and field-effect transistor characteristics in polymeric bithiophene-imide semiconductors
Electron transporting (n-channel) polymer semiconductors for field-effect transistors are rare. In this investigation, the synthesis and characterization of new electron-depleted N-alkyl-2,2′-bithiophene-3,3′- dicarboximide-based π-conjugated homopolymers and copolymers containing the 2,2′-bithiophene unit are reported. A novel design approach is employed using computational modeling to identify favorable monomer properties such as core planarity, solubilizing substituent tailorability, and appropriate electron affinity with gratifying results. Monomeric model compounds are synthesized to confirm these properties, and a crystal structure reveals a short 3.43 A π-π stacking distance with favorable solubilizing substituent orientations. A family of 10 homopolymers and bithiophene copolymers is then synthesized via Yamamoto and Stille polymerizations, respectively. Two of these polymers are processable in common organic solvents: the homopolymer poly(N-(2-octyldodecyl)-2,2′-bithiophene-3,3′-dicarboximide) (P1) exhibits n-channel FET activity, and the copolymer poly(N-(2-octyldodecyl)-2, 2′:5′,2″:5″,2?-quaterthiophene-3, 3′-dicarboximide) (P2) exhibits air-stable p-channel FET operation. After annealing, P1 films exhibit a very high degree of crystallinity and an electron mobility > 0.01 cm2 V-1 s-1 with a current on-off ratio of 107, which is remarkably independent of film-deposition conditions. Extraordinarily, P1 films also exhibit terracing in AFM images with a step height matching the X-ray diffraction d spacing, a rare phenomenon for polymeric organic semiconductors. Another fascinating property of these materials is the air-stable p-channel FET performance of annealed P2 films, which exhibit a hole mobility of ～0.01 cm2 V-1 s-1 and a current on-off ratio of 107.
Letizia, Joseph A.,Salata, Michael R.,Tribout, Caitlin M.,Facchetti, Antonio,Ratner, Mark A.,Marks, Tobin J.
experimental part
p. 9679 - 9694
(2009/02/04)

Palladium-catalyzed C-H homocoupling of bromothiophene derivatives and synthetic application to well-defined oligothiophenes
Synthesis of oligothiophenes of well-defined structures that possess 2-8 thiophene units is performed with a new synthetic strategy involving C-H homocoupling of bromothiophenes and cross-coupling with organostannanes. Tolerance of the carbon-bromine bond to the palladium-catalyzed C-H homocoupling results in oligothiophenes bearing C-Br bonds at the terminal thiophene rings, which allow further transformation by the catalysis of a transition-metal complex.
Takahashi, Masabumi,Masui, Kentaro,Sekiguchi, Hiroki,Kobayashi, Nobuhiko,Mori, Atsunori,Funahashi, Masahiro,Tamaoki, Nobuyuki
p. 10930 - 10933
(2007/10/03)

Linearly extended tetrathiafulvalene analogues with fused thiophene units as π-conjugated spacers
A new series of linearly extended tetrathiafulvalene analogues with thienothiophene and dithienothiophene π-conjugating spacers has been synthesized. Electronic absorption spectra present a vibronic fine structure typical for rigid conjugated systems. Investigation of the electrochemical behaviour of the new donors by cyclic voltammetry reveals the successive generation of stable radical cation and dication species. The crystallographic structure of a single crystal of a dication salt of TT-TTF(ClO4)2 has been analysed by X-ray diffraction. The dication presents a syn conformation stabilised by S...S intramolecular interactions. The quinoid structure expected for the spacer for the +2 oxidation state is clearly revealed by the bond lengths.
Leriche, Philippe,Raimundo, Jean-Manuel,Turbiez, Mathieu,Monroche, Vincent,Allain, Magali,Sauvage, Francois-Xavier,Roncali, Jean,Frere, Pierre,Skabara, Peter J.
p. 1324 - 1332
(2007/10/03)

Novel photoluminescent polymers containing oligothiophene and m-phenylene-1,3,4-oxadiazole moieties: Synthesis and spectroscopic and electrochemical studies
Three conjugated polymers containing oligothiophene units (from one to three thiophene rings) and aromatic 1,3,4-oxadiazole moieties have been successfully synthesized. The polymer structures were characterized and confirmed by 1H and 13C NMR, FT-IR, and elemental analysis. Thermogravimetric analysis demonstrated that the polymers are highly thermal stable. Tunable absorption (from 342 to 428 nm) and fluorescence (from 411 to 558 nm) properties of polymers were observed: The electrochemical investigation indicated that the LUMO and HOMO energy levels of the new polymers could be adjusted. It was also revealed by the electrochemical analysis that the polymers have good charge injection properties for both p-type and n-type charge carriers, as well as good color tunable luminescence and film-forming properties, which makes them potentially useful for fabricating efficient light-emitting devices.
Meng,Huang
p. 3894 - 3901
(2007/10/03)

Palladium-catalyzed syntheses of polyethynyl-substituted 2,2′-bithiophenes
The syntheses of polyethynyl-substituted 2,2′-bithiophenes 2 and related 5,5′-dicarbaldehyde derivatives 1 are described. The treatment of easily available polybrominated 2,2′-bithiophenes 3 and 2,2′-bithiophene-5,5′-dicarbaldehydes 4 with phenyl or (trimethylsilyl)acetylene in the presence of PdII and CuI in (i-Pr)2NH yields substituted polyethynyl-2,2′-bithiophene compounds. The Me3Si protecting groups can be removed by protodesilylation under basic conditions to give the corresponding terminal ethynyl groups. These polyethynyl-bithiophenes could be interesting precursors for the synthesis of macrocycles with interesting properties.
Dahlmann, Uwe,Neidlein, Richard
p. 755 - 766
(2007/10/03)

A Facile Synthetic Approach to Symmetrical 3,3'-Difunctionalised-2,2'-bithiophenes from 3,3'-Dibromo-2,2'-bithiophene
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Ng, S. C.,Chan, H. S. O.,Huang, H. H.,Seow, R. S. H.
p. 1285 - 1294
(2007/10/03)

Novel Electron Acceptors Bearing a Heteroquinonoid System. I. Synthesis and Conductive Complexes of 5,5'-Bis(dicyanomethylene)-5,5'-dihydro-Δ2,2'-bithiophene and Related Compounds
Novel electron acceptors bearing a heteroquinonoid system, 5,5'-bis(dicyanomethylene)5,5'-dihydro-Δ2,2'-bithiophene, its 3,3'-dichloro, 3,3'-dibromo, and 3,3',4,4'-tetrabromo derivatives, and 5,5''-bis(dicyanomethylene)-5,5''-dihydro-Δ2,2':5',2''-tertiophene were synthesized by the action of tetracyanoethylene oxide or by Pd(0)-catalyzed substitution reactions with sodium dicyanomethanide on the corresponding α,α'-dihalogeno-heteroaromatics.They showed very small on-site Coulomb repulsion as expected, and afforded several highly conductive molecular complexes with electron donors such as hexamethylenetetratellurafulvalene.
Yui, Koji,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
p. 1539 - 1546
(2007/10/02)