- Emission enhancement of a carbazole-based fluorophore on a quantum dot surface
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A novel carbazole-based fluorophore 5-(carbazol-9-yl)-5′-mercapto-2, 2′-bithiophene (CBTSH) was synthesized. CBTSH exhibited emission enhancement when attached to the surface of CdSe quantum dots (QDs). The emission quantum yield of CBTSH attached to CdSe is almost 5 times larger than that of CBTSH alone. The emission enhancement of CBTSH on the CdSe surface is due to the restriction on the rotational and vibrational motions of the carbazolylbithienyl unit as a result of QD aggregation.
- Kumar De, Puran,Neckers, Douglas C.
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Read Online
- Synthesis and Characterization of α,α'-Bis(aminomethyl)oligothiophenes and Their Related Compounds
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We have synthesized and characterized a series of novel compounds of α,α'-bis(aminomethyl)oligothiophenes and their related compounds whose degree of polymerization spans two (dimer) to five (pentamer). The compounds presented in our studies are α,α'-bis[(2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopenthyl)methyl] oligothiophene, α,α'-bis(aminomethyl)oligothiophene dihydrochloride and α,α'- bis(aminomethyl)oligothiophene. These compounds exhibit desired chemical activity while maintaining controllable electronic properties. The synthetic processes of the oligothiophenes are as follows: 2-aminomethylthiophene is first 'protected' and the thiophene rings are coupled using standard Grignard methods. The protected groups are removed at the final stage of the reaction. The compounds show unique properties; for example α,α'-bis(aminomethyl)oligothiophene dihydrochloride is soluble in water. The results of electronic spectra and duration are also presented.
- Muguruma, Hitoshi,Saito, Takashi,Sasaki, Satoshi,Hotta, Shu,Karube, Isao
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Read Online
- A star-shaped oligothiophene with triphenylamine as core and octyl cyanoacetate as end groups for solution-processed organic solar cells
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A new star-shaped D-π-A molecule with triphenylamine (TPA) as core and donor unit, octyl cyanoacetate (CA) as end group and acceptor unit, and 2,2′-bithiophene vinylene (bTV) as π bridge, S(TPA-bTV-CA) was designed and synthesized for the application as donor materials in solution-processed bulk-heterojunction organic solar cells (OSCs). The compound is soluble in common organic solvents. The thermal, optical and electrochemical properties of the star molecule were studied. The OSC devices were fabricated by spin-coating the blend solution of the molecule as donor and PC70BM as acceptor (1:3, w/w). The OSC device based on S(TPA-bTV-CA)/PC70BM demonstrated a high open circuit voltage of 0.91 V, a short circuit current density of 4.64 mA/cm2, a fill factor (FF) of 50%, corresponding to a power conversion efficiency of 2.1%, under the illumination of AM 1.5, 100 mW/cm 2.
- Shen, Suling,Gao, Lei,He, Chang,Zhang, Zhanjun,Sun, Qingjiang,Li, Yongfang
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- Improved synthesis of a quaterthiophene-triazine-diamine derivative, a promising molecule to study pathogenic prion proteins
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The 6,6′-([2,2′:5′,2″:5″,2-quaterthiophene]-5,5-diyl)bis(1,3,5-triazine-2,4-diamine) (MR100), has been previously investigated in our research group through its biological activities toward pathogenic prion proteins (PrPSc). This compound presents a high affinity to protein strains and interacts selectively with at least one β-sheet rich isoform of prion protein. Herein we present the improved total synthesis of MR100, through a palladium-catalyzed direct double arylation using the concerted metalation deprotonation mechanism (CMD).
- Rodrigues, Alysson Duarte,Imberdis, Thibaut,Perrier, Véronique,Robitzer, Mike
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- Synthesis of 2-Bromo-2′-phenyl-5,5′-thiophene: Suzuki reaction versus Negishi reaction
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2-Bromo-2′-phenyl-5,5′-thiophene was synthesized by cross-coupling reaction of phenylboric acid and 2,2′-dibromo-5,5′-bithiophene with a Suzuki reaction; we found the Suzuki reaction to give a higher yield when compared to the Negishi reaction.
- Wang, Nai-Xing
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Read Online
- Synthesis and structure of tetrathiophene with a chiral 1,1′-binaphthyl kink
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A chiral oligothiophene, possessing in-chain chirality, was prepared and its racemate was characterized by single crystal X-ray crystallography; the in-chain chiral 1,1′-binaphthyl moiety interrupts the π-conjugation and affects the solid state properties
- Rajca,Wang,Pawitranon,Brett,Stezowski
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Read Online
- Aryl halide and synthesis method and application thereof
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The invention discloses a synthesis method of aryl halides (including aryl bromide shown as a formula (2) and aryl iodide shown as a formula (3)). All the systems are carried out in an air atmosphere,visible light is utilized to excite a substrate or a photosensitizer to catalyze the reaction; and in a reaction solvent, when aromatic hydrocarbon shown in the formula (1) and sodium bromide serve as raw materials, aryl bromide shown in the formula (2) is obtained through a reaction under the auxiliary action of an additive (protonic acid); or when aromatic hydrocarbon shown in the formula (1) and sodium iodide are used as raw materials, under the auxiliary action of an additive (protonic acid), aryl iodide shown in the formula (3) is obtained through reaction. The synthesis method has the advantages of cheap and accessible raw materials, simple reaction operation and mild reaction conditions. The method is compatible with the arylamine which is liable to be oxidized. The invention provides a new method for the synthesis of aryl halides, realizes the amplification of basic chemicals aryl halides including aryl bromide shown in the formula (2) and aryl iodide shown in the formula (3),and has wide application prospect and practical value.
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Paragraph 0118-0120
(2020/06/02)
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- Visible-light-promoted oxidative halogenation of (hetero)arenes
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Organic halides are critical building blocks that participate in various cross-coupling reactions. Furthermore, they widely exist as natural products and artificial molecules in drugs with important physiological activities. Although halogenation has been well studied, to the best of our knowledge, studies focussing on sensitive systems (e.g.aryl amines) have not been reported. Herein, we describe a compatible oxidative halogenation of (hetero)arenes with air as the oxidant and halide ions as halide sources under ambient conditions (visible light, air, aqueous system, room temperature, and normal pressure). Moreover, this protocol is practically feasible for gram-scale synthesis, showing potential for industrial application.
- Jiang, Xuefeng,Li, Yiming,Lu, Lingling
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supporting information
p. 5989 - 5994
(2020/10/18)
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- Pd-Catalyzed Aerobic Oxidative Coupling of Thiophenes: Synergistic Benefits of Phenanthroline Dione and a Cu Cocatalyst
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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.
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supporting information
p. 20318 - 20323
(2020/12/01)
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- Sterically controlled C-H/C-H homocoupling of arenes: Via C-H borylation
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A mild one-pot protocol for the synthesis of symmetrical biaryls by sequential Ir-catalyzed C-H borylation and Cu-catalyzed homocoupling of arenes is described. The regiochemistry of the biaryl formed is sterically controlled as dictated by the C-H borylation step. The methodology is also successfully extended to heteroarenes. Some of the products obtained by this approach are impossible to obtain via the Ullmann or the Suzuki coupling protocols. Finally, we have shown a one-pot sequence describing C-H borylation/Cu-catalyzed homocoupling/Pd-catalyzed Suzuki coupling to obtain π-extended arene frameworks.
- Pei, Xiaocong,Zhou, Guan,Li, Xuejing,Xu, Yuchen,Panicker, Resmi C.,Srinivasan, Rajavel
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supporting information
p. 5703 - 5707
(2019/06/19)
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- Synthesis and characterization of new D-π-A and A-π-D-π-A type oligothiophene derivatives
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In this work, we present a series of newly synthesized conjugated oligothiophene derivatives, with different numbers of central thiophene units, and different donor/acceptor architectures. Electrochemical and spectroscopic data have also been reported. We used thiophene or bithiophene as central donor core units, 3-octylthiophenes as π-bridge and solubilizing sub-units, and ethyl cyanoacetate or rhodanine moieties as acceptor end groups, in order to get D-π-A and A-π-D-π-A molecular architectures. The length of the synthesized oligothiophenes ranges from three to eight thiophene units, a variety that is sufficient to put in evidence different optical and electrochemical characteristics as well as semiconducting characteristics. Oligothiophene compounds can be regarded not only as models for the study of structure-property relationships relative to polythiophenes, but also they present a large number of applications in the field of organic electronics (i.e.: as donors in bulk-heterojunction solar cells and hole-transporting layer materials in perovskite solar cells, among others).
- Pandolfi, Fabiana,Rocco, Daniele,Mattiello, Leonardo
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supporting information
p. 3018 - 3025
(2019/03/21)
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- Synthesis and characterization of poly(tetramethylsilarylenesiloxane) derivatives with oligothiophene based moiety
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Poly(tetramethylsilarylenesiloxane) derivatives (P1T-P4T, P4TC) that contained thiophene (1T), oligothiophenes such as dithiophene (2T), terthiophene (3T), quaterthiophene (4T), or 2,6-di(2-thienyl)-4,4-diphenylcyclopentadithiophene (4TC) as the main chain components were synthesized via polycondensation reaction of the corresponding disilanol monomers (M1T-M4T, M4TC). The obtained polymers other than P4T that contained quaterthiophene units exhibited the good solubility in common organic solvents, such as toluene, chloroform, tetrahydrofuran and so on. The glass transition temperature (Tg) and melting temperature (Tm) of the obtained polymers regarding P1T-P4T were increased with the extension of the thiophene rings of the monomeric unit as deduced from the results of the differential scanning calorimetry (DSC). On the other hand, the Tm was not observed for P4TC that was composed of 2,6-di(2-thienyl)-4,4-diphenylcyclopentadithiophene units. P2T that was composed of dithiophene units exhibited the highest temperature at 5% weight loss (Td5) of 467 °C in all present polymers. The bathochromic and hyperchromic effects in the absorption spectra as well as the improvement of fluorescence quantum yield were observed by the introduction of dimethylsilyl group onto the present oligothiophene derivatives. These effects became unremarkable accompanying the elongation of the thiophene rings of the monomeric units; however, 4TC exhibited a more significant change by the introduction of the dimethylsilyl group than the other oligothiophenes derivatives, indicating that the introduction of the cardo-structure was effective in the improvement of the optical properties. M4TC and P4TC exhibited the fluorescence wavelength around 500 nm and the highest fluorescence quantum yield of the present series of poly(tetramethylsilarylenesiloxane) derivatives, i.e., 0.40, plausibly because the free rotation between thiophene rings in oligothiophene inhibited by the cardo-structures and the bulky diphenyl groups at 4-position of cyclopentadithiophene moiety suppressed the nonradiative transition.
- Nishizawa, Ibuki,Ajito, Hiroki,Gonmori, Yuzuki,Katoh, Ryuzi,Ichikawa, Tsukasa,Nemoto, Nobukatsu
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- ORGANIC COMPOUND, ORGANIC THIN FILM, AND ELECTRONIC DEVICE
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Disclosed are an organic compound selected from a compound represented by Chemical Formula 1A, a compound represented by Chemical Formula 1B, and a combination thereof, an organic thin film including the organic compound, an organic thin film transistor, and an electronic device. The organic compound has liquid crystal properties and exhibits an ordered liquid crystal phase when being heated in a liquid crystal period due to asymmetric substituents and thereby charge mobility may be further improved.
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Paragraph 0219; 0220; 0221
(2019/02/09)
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- Superelectrophilic-initiated C-H functionalization at the β-position of thiophenes: A one-pot synthesis of trans-stereospecific saddle-shaped cyclic compounds
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Superelectrophilic-initiated direct C-H functionalization of thiophenes at the β-position was developed. A series of trans-stereospecific [2,1-a]-IF-thiophene-fused cyclic compounds (4) with saddle-shaped structure were prepared in 17-30% yields through a
- Wei, Ying,Zheng, Xiangping,Lin, Dongqing,Yuan, Haoxuan,Yin, Zhipeng,Yang, Lei,Yu, Yang,Wang, Shasha,Xie, Ling-Hai,Huang, Wei
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p. 10701 - 10709
(2019/09/09)
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- Non-Fullerene Small Molecule Acceptors Containing Barbituric Acid End Groups for Use in High-performance OPVs
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We synthesized two new bithiophene-based small molecules, TT-BBAR, and TT-OBAR, having butyl- and octyl-substituted barbituric acid (BAR) groups, respectively, via a well-known synthetic method, the Knoevenagel condensation, in high yield. These small mol
- Choe, Jong-chan,Lee, Tae Ho,Lim, Eunhee
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supporting information
p. 20 - 23
(2018/12/11)
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- Method for Aerobic Oxidative Coupling of Thiophenes with a Ligand-Supported Palladium Catalyst
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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; 0108; 0129-0132
(2019/07/23)
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- A molecular structure and crystallization correlation study of pyromellitic diimide-based conjugated copolymers
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Three pyromellitic diimide(PMDI)-based polymers—poly(pyromellitic diimide-co-bithiophene) [poly(PMDI-BTh)], poly(pyromellitic diimide-co-tetrathiophene) [poly(PMDI-TTh)], and poly(pyromellitic diimide-co-benzodithio- phene) [poly(PMDI-BDTTh)]—are synthesized to study the influence of different thiophene-containing electron-donating groups on the crystallizability of PMDI-based conjugated polymers. Computer simulation using Density Functional Theory (DFT) [Gaussian B3LYP/6–31 + G(d,p)] indicates that poly(PMDI-BDTTh) has a more planar molecular structure than the other two copolymers. Powder XRD diffraction experiment of the poly(PMDI-BDTTh) shows a diffraction peak at about 2θ = 6.0°, but no diffraction peak occurs for poly(PMDI-BTh) and poly(PMDI-TTh). Although PMDI is a planar structure that is favorable for the molecular aggregation, a comonomer with planar structure seems to be very crucial in order to synthesize a crystallizable push–pull-type PMDI-based conjugated copolymer.
- Tsai, Ming-Chia,Liu, Ja-Wei,Huang, Ping-Tsung
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p. 828 - 834
(2018/03/21)
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- Oligothiophene compounds inhibit the membrane fusion between H5N1 avian influenza virus and the endosome of host cell
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Hemagglutinin (HA) which is essential for influenza viral infection and replication has become a target for the design of anti-influenza drugs. A novel series of oligothiophene compounds focused on the target were synthesized as specific inhibitors agains
- Zhu, Zhibo,Liu, Shuwen,Yao, Zhili,Shen, Xiantian,Chen, Zhipeng,Liu, Xiangtao,Parquette, Jon R.,Liu, Shuwen
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p. 185 - 194
(2017/03/08)
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- Benzocarbazoles three thiophene compound and its preparation and use
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The invention relates to benzo terthiophene compound as well as a preparation method and usage thereof. The structure of the benzo terthiophene compound is expressed by a formula I, and in the formula, the definition of X is described in the description.
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Paragraph 0237-0239
(2016/11/07)
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- Synthesis and characterization of two new benzothiadiazole- and fused bithiophene based low band-gap D-A copolymers: Application as donor bulk heterojunction polymer solar cells
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Two new narrow bandgap D-A conjugated copolymers P1 and P2 containing different fused thiophene donor unit and same benzothiadiazole acceptor unit were synthesized by Stille cross-coupling polymerization, and characterized by 1H NMR, elemental analysis and GPC, TGA, DSC. Cyclic voltammetry measurement showed that the HOMO energy level both copolymers is deep lying (-5.10 and -5.35 eV for P1 and P2, respectively) which show that copolymers has good stability in the air and assured a higher open circuit voltage when it photovoltaic application. These copolymer were used as donor along with PC71BM and the BHJ polymer solar cells based on P1:PC71BM and P2:PC71BM processed with chloroform (CF) solvent showed over all PCE of 4.54% and 4.36%, respectively. Additionally, the PCE was improved up to 5.62% and 5.24% for P1:PC71BM and P2:PC71BM active layer processed with DIO (4 v%)/CF solvent. The enhancement in the PCE has been attributed to improved nanoscale morphology and crystalline nature of active layer as well as charge transport in the device with the addition of DIO, due to the higher boiling point of DIO causing slow evaporation rate during the film formation.
- Keshtov,Sharma,Kuklin,Ostapov,Godovsky,Khokhlov,Chen
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p. 193 - 201
(2016/01/30)
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- Convenient synthesis of organic-electronics-oriented building blocks via on-water and under-air homocoupling of (hetero)aryl iodides
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We report herein an operationally simple homocoupling reaction that targets the convenient synthesis of organic-electronically important building blocks. A variety of synthetically useful bithiophene derivatives and functionalized biphenyls are efficiently prepared by an on-water and under-air protocol using Pd/C as catalyst. We find that Pd/C gives generally higher and cleaner homocoupling conversions than using Pd(OAc)2 in the cases of (hetero)aryl iodides since Pd(OAc)2 triggers more side reactions including dehalogenations and oligomerizations. Under the optimum conditions, a broad range of functional groups such as ester, ketone, aldehyde, nitrile, nitro, chloride, and bromide are well tolerated. We expect the present methodology would make a valuable synthetic contribution towards bridging green chemistry with thiophene-based organic materials.
- Chen, Yi-An,Liu, Ching-Yuan
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p. 74180 - 74188
(2015/09/21)
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- 5,5′-Bis-(alkylpyridinyl)-2,2′-bithiophenes: Synthesis, liquid crystalline behaviour and charge transport
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Liquid crystalline materials with 5,5′-bis-(alkylpyridinyl)-2, 2′-bithiophene structures with different positions of the nitrogen atoms in the aromatic core were synthesized, characterized by differential scanning calorimetry, polarized optical microscopy and, in some cases, by synchrotron X-ray diffraction analysis and single crystal X-ray analysis. The molecular planarity and liquid crystalline (LC) behaviour of these materials are strongly influenced by the location of the nitrogens in the aromatic core, and LC behaviour is more complex than the mesomorphic behaviour of the known structurally related 5,5′-bis-(alkylphenyl)-2,2′-bithiophene LCs. Single crystal X-ray structural analysis of 5,5′-bis-(5-alkylpyridin-2-yl) -2,2′-bithiophenes 2 reveals that the aromatic core is nearly planar with s-cis conformation of the thiophene and pyridine rings and s-trans conformation of the thiophene rings of the central 2,2′-bithiophene unit. The length of the alkyl chains has a pronounced effect on the molecular planarity and the packing motifs. A preliminary study of the charge-transporting properties of 5,5′-bis-(5-alkylpyridin-2-yl)-2,2′-bithiophenes 2d and 2e with n-nonyl and n-decyl alkyl chains, respectively, by the time-of-flight technique shows that the hole mobility is temperature independent, electric field dependent and with a magnitude of ～1.5 × 10-4 cm 2 V-1 s-1 in the unidentified S2/Cr2 phase. The Royal Society of Chemistry.
- Getmanenko, Yulia A.,Kang, Shin-Woong,Shakya, Naresh,Pokhrel, Chandra,Bunge, Scott D.,Kumar, Satyendra,Ellman, Brett D.,Twieg, Robert J.
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p. 256 - 271
(2014/01/06)
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- Gold-catalyzed oxidative coupling of arylsilanes and arenes: Origin of selectivity and improved precatalyst
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The mechanism of gold-catalyzed coupling of arenes with aryltrimethylsilanes has been investigated, employing an improved precatalyst (thtAuBr3) to facilitate kinetic analysis. In combination with linear free-energy relationships, kinetic isotope effects, and stoichiometric experiments, the data support a mechanism involving an Au(I)/Au(III) redox cycle in which sequential electrophilic aromatic substitution of the arylsilane and the arene by Au(III) precedes product-forming reductive elimination and subsequent cycle-closing reoxidation of the metal. Despite the fundamental mechanistic similarities between the two auration events, high selectivity is observed for heterocoupling (C-Si then C-H auration) over homocoupling of either the arylsilane or the arene (C-Si then C-Si, or C-H then C-H auration); this chemoselectivity originates from differences in the product-determining elementary steps of each electrophilic substitution. The turnover-limiting step of the reaction involves associative substitution en route to an arene π-complex. The ramifications of this insight for implementation of the methodology are discussed.
- Ball, Liam T.,Lloyd-Jones, Guy C.,Russell, Christopher A.
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supporting information
p. 254 - 264
(2014/01/23)
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- One-pot, regioselective consecutive multihalogenation of 2,2′-bithiophene
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The one-pot regioselective consecutive multihalogenation of 2,2′-bithiophene (1) was demonstrated. Compound 1 was consecutively halogenated with lithium halides such as lithium bromide, chloride, and/or iodide in the presence of lead tetraacetate in chloroform at room temperature or under reflux conditions to give 5-bromo(or chloro)-5′-iodo(or chloro)-, 3-bromo(or chloro)-5,5′-dibromo(or dichloro, diiodo)-, 3,3′-dibromo-(or dichloro)-5,5′-diiodo(or dibromo, dichloro)-, and 3,3′,5-tribromo(or trichloro)-5′-iodo(or bromo)-2,2′- bithiophenes. Notably, this process offers a regioselective method for consecutive multihalogenation in one pot, and the yields and selectivity are also higher than those obtained in the step-by-step and concurrent halogenation methods. Copyright
- Kim, Bo Ram,Kim, Eun Jung,Sung, Gi Hyeon,Kim, Jeum-Jong,Shin, Dong-Soo,Lee, Sang-Gyeong,Yoon, Yong-Jin
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supporting information
p. 2788 - 2791
(2013/06/27)
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- Green halogenation of aromatic heterocycles using ammonium halide and hydrogen peroxide in acetic acid solvent
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The green generation of X+ (X = Br, I) using hydrogen peroxide in aqueous acetic acid allows access to aromatic heterocyclic halides in yields and purities comparable to syntheses employing N-bromosuccinimide. In activated and unsubstituted thiophene rings, regioselectivity is quantitative for positions α to the sulfur; pyrroles also give quantitative reactions, at least initially. Deactivated rings, including furans and thiazoles, as well as thiophenes with strongly electron-withdrawing groups showed little to no reactivity under the conditions investigated. The reaction shows remarkable functional group tolerance (to alcohol, nitro, alkyl, halo, and carbonyl groups), as shown through reaction with substituted phenols. In all bromination reactions, reaction yields and regiochemistry were very similar to reactions involving N-bromosuccinimide in tetrahydrofuran solvent.
- D'Aleo, Danielle N.,Allard, Sheena R.,Foglia, Cassandra C.,Parent, Shawna L.M.,Rohr, David J.,Gottardo, Christine,MacKinnon, Craig D.
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supporting information
p. 679 - 683
(2013/08/23)
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- Effect of side-chain architecture on the optical and crystalline properties of two-dimensional polythiophenes
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The present study reported here synthesis of three novel two-dimensional (2D) polythiophene derivatives with conjugated terthiophene-vinylene side chain - poly{3-(5″-hexyl-2,2′:5′,2″-terthiophenyl-5-vinyl) thiophene-alt-thiophene} (P1), poly{3-(5,5″-dihexyl-2,2′:5′, 2″-terthiophenyl-3′-vinyl)thiophene-alt-thiophene} (P2), and poly{3-(4,4″-dihexyl-2,2:5′,2″-terthiophene-3′-vinyl) thiophene-alt-thiophene} (P3) - that were synthesized via stille coupling reaction. The terthiophene side chain with different conformations conjugated to the polythiophene main chain via vinyl linkage provided the ability to control the molecular organization, hence affecting the optoelectronic and electrochemical properties of 2D polymers. TD-DFT calculation with the B3LYP/6-31+g(d) function on electronic structures of the monomers was consistent with the experimental results. It suggested that the energetic states of HOMO and LUMO were highly dependent on the side-chain architectures. These polythiophene thin films fabricated by spin-casting show a broader absorption ranges from 300 to 700 nm which was significantly wider than the absorption of pure poly(3-hexylthiophene). When comparing the solid-state absorption spectra of these polymers before and after thermal annealing, P3 displayed the most red-shift in the wavelength range between 450 and 700 nm. It was presumably due to an extended conjugation length resulting from the linear conformation and preferred chain packing, as manifested in the X-ray diffraction. Molecular dynamics (MD) simulation on polymers with different side chains in isolated and packed states suggests planar conformation of the main chain was adopted and regulated by the side chains which were placed in parallel with the main-chain direction. Interestingly, P1 solution revealed an excitation-dependent emission property, suggesting a structural inhomogeneity in solution. Contrary to P1, the PL spectra of P2 and P3 showed only one emission peak at 460 nm, regardless of the excitation energy. Orientation and regiochemistry of the terthiophene side chain had a major impact on the overall optical and electronic properties of the polymer. Moreover, the HOMO and LUMO of these three polymers had been determined through cyclic voltammetry. HOMO of the three polymers were in the following order: P1 > P2 > P3. It implied that the energy level was regiochemistry dependent and directly associated with the linked position between backbone and conjugated side chain. Most importantly, through mesogen-jacketed-like design strategy employed in the present study, the improved packing of these two-dimensional polymers offered insights into structure design to enhance properties that have strong ties to the electronic devices.
- Kuo, Cheng-Yu,Huang, Yu-Chen,Hsiow, Chuen-Yo,Yang, Yu-Wen,Huang, Ching-I,Rwei, Syang-Peng,Wang, Hsing-Lin,Wang, Leeyih
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p. 5985 - 5997
(2013/09/02)
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- Molecular aggregation-performance relationship in the design of novel cyclohexylethynyl end-capped quaterthiophenes for solution-processed organic transistors
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The synthesis and characterization of cyclohexylethenyl end-capped quaterthiophenes is reported. Additionally, an investigation of the performance of organic field-effect transistors based on these quaterthiophenes in view of the relationship between the solid-state (or aggregate) order and the electronic performance is described. UV-vis absorption measurements revealed that the quaterthiophene with an asymmetrically substituted cyclohexylethynyl end-group induced the formation of H-type aggregates, whereas the quaterthiophene with a symmetrically substituted cyclohexylethynyl end-groups favored the formation of J-type aggregates. Two-dimensional grazing-incidence wide-angle X-ray scattering studies were performed to support the molecular structure-dependent packing of films of the new quaterthiophenes. Solution-processed quaterthiophenes were tested as the active layers of p-type organic field-effect transistors with a bottom gate/top contact geometry. The field-effect mobility of devices that incorporated asymmetric quaterthiophene molecules was quite high, exceeding 0.02 cm2/V s, due to H-aggregation and good in-plane ordering. In contrast, the field-effect mobility of devices that incorporated symmetrical quaterthiophenes, was low, above 5 × 10-4 cm2/(V s), due to the formation of J-aggregates and poor in-plane ordering. A comparison of the symmetrical and asymmetrical quaterthiophene derivatives revealed that the molecular aggregation-dependent packing, determined by the cyclohexylethynyl end groups, was responsible for influencing the organic field-effect transistor performance.
- An, Tae Kyu,Hahn, Seung-Hoon,Nam, Sooji,Cha, Hyojung,Rho, Yecheol,Chung, Dae Sung,Ree, Moonhor,Kang, Moon Seong,Kwon, Soon-Ki,Kim, Yun-Hi,Park, Chan Eon
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p. 756 - 762
(2013/03/13)
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- Pd-catalyzed oxidative cross-coupling between two electron rich heteroarenes
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The transition-metal-catalyzed oxidative cross-coupling between two coupling partners with similar structure and electronic characteristics remains a challenge owing to difficulty in suppressing undesired homo-couplings. We herein report a Pd-catalyzed oxidative cross-coupling between two thiophenes under mild reaction conditions. This approach can also be extended to furans. Some notable advantages of this reaction lie in its synthetic simplicity with the omission of the toxic stannanes coupling partner and excellent functional-group compatibility. The features of this protocol make it an ideal strategy for the construction of a 2,2′-thiophene-thiophene linkage of interest in electronic and optoelectronic materials.
- He, Chun-Yang,Wang, Zhen,Wu, Cai-Zhi,Qing, Feng-Ling,Zhang, Xingang
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p. 3508 - 3513
(2013/11/19)
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- PROCESS FOR PRODUCTION OF OXIDATION REACTION PRODUCT OF AROMATIC COMPOUND
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The present invention provides a process for producing an oxidation reaction product of an aromatic compound, having excellent environmental load reduction performance, cost reduction performance, etc. Provided is a process for producing an oxidation reaction product of a raw material aromatic compound by reacting the raw material aromatic compound with an oxidizing agent. The process further uses an electron donor-acceptor linked molecule. The process includes the step of: reacting the electron donor-acceptor linked molecule in an electron-transfer state, the oxidizing agent, and the raw material aromatic compound, thereby generating an oxidation reaction product resulting from oxidation of the raw material aromatic compound.
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Page/Page column 19
(2012/07/14)
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- Hydrophilicity control of visible-light hydrogen evolution and dynamics of the charge-separated state in dye/TiO2/Pt hybrid systems
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Visible-light-driven H2 evolution based on Dye/TiO 2/Pt hybrid photocatalysts was investigated for a series of (E)-3-(5'-{4-[bis(4-R1-phenyl)amino]phenyl}-4,4'-(R2) 2-2,2'-bithiophen-5-yl)-2-cyanoacrylic acid dyes. Efficiencies of hydrogen evolution from aqueous suspensions in the presence of ethylenediaminetetraacetic acid as electron donor under illumination at λ>420 nm were found to considerably depend on the hydrophilic character of R1, varying in the order MOD (R1=CH 3OCH2, R2=H)≈MO4D (R1=R 2=CH3OCH2)>HD (R1=R 2=H)>PD (R1=C3H7, R 2=H). In the case of MOD/TiO2/Pt, the apparent quantum yield for photocatalyzed H2 generation at 436 nm was 0.27A±0.03. Transient absorption measurements for MOD- or PD-grafted transparent films of TiO2 nanoparticles dipped into water at pH 3 commonly revealed ultrafast formation (.+) followed by multicomponent decays, which involve minor fast decays (1 and major slower decays with significant differences between the two samples: 1) the early decay of the major components for MOD is about 2.5 times slower than that for PD and 2) a redshift of the spectrum occurred for MOD with a time constant of 17 ps, but not for PD. The substituent effects on H2 generation as well as on transient behavior have been discussed in terms substituent-dependent charge recombination (CR) of Dye.+ with electrons in bulk, inner-trap, and/or interstitial-trap states, arising from different solvent reorganization. Photosensitized H2 generation by a series of Dye/TiO2/Pt hybrids revealed clear dependence on the hydrophilic/hydrophobic character of the substituent R of Dye (see figure; I(H2)=apparent quantum yield for H2 generation.), which was shown by femtosecond transient spectroscopy to arise from the hydrophilic control of charge recombination (CR) between Dye.+ and the injected electron TiO2(e -). Copyright
- Han, Won-Sik,Wee, Kyung-Ryang,Kim, Hyun-Young,Pac, Chyongjin,Nabetani, Yu,Yamamoto, Daisuke,Shimada, Tetsuya,Inoue, Haruo,Choi, Heesung,Cho, Kyeongjae,Kang, Sang Ook
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p. 15368 - 15381
(2013/01/15)
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- 2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4-(2H,5H)-dione-based donor-acceptor alternating copolymer bearing 5,5′-Di(thiophen-2-yl)-2, 2′-biselenophene exhibiting 1.5 cm2·V -1·s-1 hole mobility in thin-film transistors
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A novel diketopyrrolopyrrole-based π-conjugated copolymer P(DPP-alt-DTBSe), 5, and a known copolymer P(DPP-alt-QT), 4, have been synthesized in 80-90% yield using the Stille coupling reaction. The molecular weights of 4 and 5 are 58 781 and 19 271 g/mol, respectively, with polydispersity values of 3.25-3.35. A relatively small band gap of 1.32-1.39 eV and excellent solubility in organic solvents were achieved in the two polymers. Thin-film transistors made of 5 exhibit outstanding performance (e.g., μ > 1.0-1.5 cm2·V-1·s-1, I on/Ioff > 105-106) with a conventional n-octyltrichlorosilane-SiO2 gate dielectric.
- Ha, Jae Seung,Kim, Kyung Hwan,Choi, Dong Hoon
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supporting information; scheme or table
p. 10364 - 10367
(2011/09/13)
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- Direct alkynylation of thiophenes: Cooperative activation of TIPS-EBX with gold and Bronsted acids
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United we stand! Cooperative activation of the hypervalent-iodine reagent TIPS-EBX with a gold catalyst and a Bronsted acid allowed the first direct ethynylation of thiophenes at room temperature (see scheme; TFA = trifluoroacetic acid). The obtained ethynylthiophenes are important building blocks for organic dyes and electronic materials.
- Brand, Jonathan P.,Waser, Jerome
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supporting information; experimental part
p. 7304 - 7307
(2010/11/05)
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- A novel method for the bromination of thiophenes
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A novel, fast and convenient method for the bromination of thiophenes and oligothiophenes with N-bromosuccinimide (NBS) using ultrasonic irradiation is elaborated. The yield of bromothiophenes strongly depends on the initial thiophene structure and nature of the solvent.
- Arsenyan, Pavel,Paegle, Edgars,Belyakov, Sergey
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scheme or table
p. 205 - 208
(2010/03/24)
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- Monodispersed molecular donors for bulk hetero-junction solar cells: From molecular properties to device performances
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The relations between the chemical-physical properties of novel designed monodispersed donors and their photovoltaic performances are discussed. The importance of intermolecular interactions is emphasized to figure out the achievement of high performing bulk hetero-junction solar cells which are solution processed.
- Colella, Silvia,Mazzeo, Marco,Grisorio, Roberto,Fabiano, Eduardo,Melcarne, Giovanna,Carallo, Sonia,Angione, M. Daniela,Torsi, Luisa,Suranna, Gian Paolo,Della Sala, Fabio,Mastrorilli, Piero,Gigli, Giuseppe
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supporting information; experimental part
p. 6273 - 6275
(2010/10/02)
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- Selective halogenation of bithiophenes using 2-halopyridazin-3(2H)-ones under ambient conditions
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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
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experimental part
p. 490 - 494
(2009/08/09)
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- Unprecedented Negishi coupling at C-Br in the presence of a stannyl group as a convenient approach to pyridinylstannanes and their application in liquid crystal synthesis
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(Chemical Equation Presented) The 2-bromo-5(or 6)-tri-n- butylstannylpyridines, prepared from dibromopyridines and i-PrMgCl at room temperature, undergo Negishi coupling with either alkyl or arylzinc chlorides. The new alkyl- and aryl-substituted pyridylstannanes produced are shown to be suitable for further functionalization by Stille coupling. A group of new liquid crystalline materials with aromatic cores comprised of pyridine and thiophene rings were prepared utilizing these new pyridinylstannanes as key intermediates.
- Getmanenko, Yulia A.,Twieg, Robert J.
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p. 830 - 839
(2008/09/18)
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- NOVEL ORGANIC SEMICONDUCTOR COMPOUND, AND ORGANIC THIN FILM TRANSISTOR USING THE SAME
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The present invention relates to novel mono- molecular organic semiconductor compounds and organic thin film transistors comprising the same. The organic semiconductor compounds according to the present invention are characterized by a structure of an acene derivative substituted with acetylene groups at both ends, a structure of anthracene derivative substituted with acetylene groups, or a structure of a multi-nuclear aromatic derivative functionalized by naphthalene having an electron-donor substituent at both ends.
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Page/Page column 46
(2008/12/04)
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- METHOD FOR THE PREPARATION OF A COMPOUND OF THE GENERAL FORMULA R1-R1 AND/OR R1-R2 USING HOMO AND HETERO COUPLING REACTIONS
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The present application relates to a method for the preparation of a compound of the general formula R1-R2 (I) and/or R1-R1 (II) comprising providing a compound of the general formula R1dM1Am.zM4Zn (III) or R1R2M1R3kAm.xM4Zn (IV) or R1M1R2R3kM2Am.xM4Zn (V) or R1M3R2M1.xM4Zn (VI) and reacting this compound III-VI with a quinone to produce a compound of the general formula (I) or (II) or a mixture of compounds (I) and (II). The coupling reaction can be used to prepare homo and/or hetero coupling products from well known starting materials using a quinone as redox reagent. The quinone may be recycled from the reaction.
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Page/Page column 3-4
(2010/11/29)
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- Transition-metal-free homocoupling of organomagnesium compounds
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(Chemical Equation Presented) Without palladium or copper: A wide range of functionalized Grignard compounds were coupled by using diphenoquinone 1 as an electron acceptor. The oxidative dimerization of alkenylmagnesium reagents proceeds with complete retention of the stereochemistry (see scheme; TBDMS = tert-butyldimethylsilyl).
- Krasovskiy, Arkady,Tishkov, Alexander,Del Amo, Vicente,Mayr, Herbert,Knochel, Paul
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p. 5010 - 5014
(2007/10/03)
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- Palladium-catalyzed C-H homocoupling of bromothiophene derivatives and synthetic application to well-defined oligothiophenes
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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
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p. 10930 - 10933
(2007/10/03)
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- Soluble variable color carbazole-containing electrochromic polymers
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Three new carbazole-containing polymers were synthesized through Suzuki cross-coupling between N-octylcarbazole-3,6-bis(ethyleneboronate) (NOctCz(BO2Et)2) and several arylene dibromides. 2,5-Dibromothiophene (DBT), 2,2′-dibromo-5,5′-bithiophene (DEBT), and 4,7-dibromo-2,1,3-benzothiadiazole (DBBTD) gave the three polymers PCzTh, PCzBi, and PCzBTD, respectively. Cyclic voltammetry showed two separate redox processes for each polymer, PCzTh (E1/2 = 0.33 V and E1/2 = 0.65 V vs Fc/ Fc+), PCzBi (E1/2 = 0.32 V and E 1/2 = 0.60 V vs Fc/Fc+), and PCzBTD (E1/2 = 0.56 V and E1/2 = 0.84 V vs Fc/Fc+). The two redox couples signify the presence of stable radical cation and dication oxidation states. In addition, the three materials were observed to display electrochromic properties. UV/vis/NIR absorbance spectroscopy revealed that each of the polymers displayed a unique absorbance maximum (345 nm for PCzTh, 375 nm for PCzBi, and 460 nm for PCzBTD) in their neutral states. Spectroelectrochemical analyses demonstrated that the π to π* transition was depleted upon application of increasingly positive potentials, giving rise to color changes. The different color states were quantified by colorimetry. PCzTh exhibits a yellow neutral state, a faint green radical cation state, and a pink dication state. PCzBi is yellow in its neutral state, light orange as a radical cation, and gray when fully oxidized. PCzBTD is orange when neutral, green-gray at intermediate potentials, and slate-gray as a dication.
- Witker, David,Reynolds, John R.
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p. 7636 - 7644
(2008/02/01)
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- Palladium-catalyzed coupling reactions of bromothiophenes at the C-H bond adjacent to the sulfur atom with a new activator system, AgNO3/KF
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(Chemical Equation Presented) Bromothiophene derivatives react with aryl iodides catalyzed by a palladium complex in the presence of a silver(I) nitrate/potassium fluoride system to induce coupling at the C-H bond, while the carbon-bromine bond is intact.
- Kobayashi, Kei,Sugie, Atsushi,Takahashi, Masabumi,Masui, Kentaro,Mori, Atsunori
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p. 5083 - 5085
(2007/10/03)
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- Palladium-Catalyzed C-H Homocoupling of Thiophenes: Facile Construction of Bithiophene Structure
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Palladium-catalyzed C-H homocoupling of thiophene derivatives takes place in the presence of silver(I) fluoride or acetate. A variety of bithiophenes are obtained in good to excellent yields. In particular, the reaction of 2-bromothiophene proceeds at room temperature to afford 5,5′-dibromo-2,2′-bithiophene, where the bromine atom is completely intact in the palladium-catalyzed reaction. XRD analysis reveals that silver fluoride is reduced to silver(0) during the reaction. Copyright
- Masui, Kentaro,Ikegami, Haruka,Mori, Atsunori
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p. 5074 - 5075
(2007/10/03)
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- Synthesis of extended α,α'-oligo(silylthiophenes) by cerium(IV) oxidative coupling reactions
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Cerium(IV) oxidative dimerisations of 4,4'-bis(trimethylsilyl)-2,2':5',2''-terthiophene and the quaterthienyl analogue 1c gave the corresponding sexi- and octi-thiophenes; the latter have been used to prepare α-linked hexadecithiophene and tetracosithiophene derivatives.
- Mustafa, Ali H.,Shepherd, Michael K.
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p. 2743 - 2744
(2007/10/03)
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- Synthesis of substituted oligothiophenes and X-ray crystal structures of 3′-methyl-2,2′:5′,2″-terthiophene, 3,3″-dimethyl-2,2′:5′,2″-terthiophene and 5′-(2-thienyl)-2,2′:3′,2″-terthiophene
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A range of substituted oligothiophenes has been prepared and characterised. Crystal structures were determined for three substituted terthiophenes. Both in solution and in the solid state, syn-conformers were found to be populated to a greater extent than expected.
- Chaloner, Penny A.,Gunatunga, Sumudu R.,Hitchcock, Peter B.
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p. 1597 - 1604
(2007/10/03)
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- Palladium-catalyzed syntheses of polyethynyl-substituted 2,2′-bithiophenes
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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
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p. 755 - 766
(2007/10/03)
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- Bipyridyl-oligothiophene derivatives as electron-conducting materials
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The invention relates to an electron-conducting molecular preparation designed to act as a conductor by receiving an electron at its one end and conducting the electron along its molecular structure to its other end. The molecule in the preparation has the following general formula (I): wherein n represents an integer from 1 to 12 the groups X and Y are identical or different and denote functional substituents bound to the pyridine nitrogen, or one or both of X and Y are absent, and R, being identical or different, represent a hydrogen atom or an aliphatic side chain introduced for enhancing the solubility of the molecule in organic solvents, for example a branched or unbranched alkyl or alkoxy group containing any number of carbon atoms. The molecular preparations can be incorporated in a substantially insulating membrane to act as conductors between an electroactive species and an electrode in diagnostic determinations.
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- Preparation of extended di(4-pyridyl)thiophene oligomers
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Different methods for the coupling of 2-(4-pyridyl)thiophene to α-dibrominated thiophene oligomers and their efficiency to produce a homologous series of extended di(4-pyridyl)thiophene oligomers have been studied. The coupling was found to be most efficient with the organozinc derivative of 2-(4-pyridyl)thiophene, using a Pd(dppf) complex as the catalyst in the coupling reaction. The resulting compounds are promising new models for trans-membrane molecular conductors.
- Alberst, Willem M.,Canters, Gerard W.,Reedijk, Jan
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p. 3895 - 3904
(2007/10/02)
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