- Cross-Coupling Polymerization of Organosodium for Polythiophene Synthesis
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Treatment of 2-chloro-3-hexylthiophene with sodium 2,2,6,6-tetramethylpiperidin-1-yl (TMPNa) in hexane resulted in deprotonation at the 5-position to afford the thiophene-sodium species, whose formation was confirmed by quenching with iodine, leading to 2-chloro-3-hexyl-5-iodothiophene in 85% yield. Addition of a nickel catalyst bearing an N-heterocyclic carbene (NHC) to the thus-formed thiophene-sodium species in cyclopentyl methyl ether induced a cross-coupling polymerization at -20 °C. After the reaction mixture was stirred for 24 h, poly(3-hexylthiophen-2,5-diyl) was obtained in 56% yield. The average molecular weight Mn was revealed to be 9700, which was close to the theoretical molecular weight (M = 8500) on the basis of the monomer feed/catalyst loading ratio (2.0 mol %), and the molecular weight distribution was found to be 2.1.
- Horie, Masaki,Inoue, Tomoki,Mori, Atsunori,Okano, Kentaro,Sakagami, Yuma,Yamamoto, Sonoka
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supporting information
p. 3506 - 3510
(2021/11/12)
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- Aggregation induced emission-emissive stannoles in the solid state
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The optoelectronic and structural properties of six stannoles are reported. All revealed extremely weak emission in solution at 295 K, but intensive fluorescence in the solid state with quantum yields (ΦF) of up to 11.1% in the crystal, and of up to 24.4% (ΦF) in the thin film.
- Lork, Enno,Ramirez Y Medina, Isabel-Maria,Rohdenburg, Markus,Staubitz, Anne
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supporting information
p. 9775 - 9778
(2020/09/07)
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- Organic Dye and Dye-Sensitized Solar Cell
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PURPOSE: An organic dye, photoelectric diode including the same and dye-sensitized solar battery are provided to have an absorbing band in long wavelength. CONSTITUTION: An organic dye is represented by chemical formula 1. A photoelectric diode includes porous oxide semiconductor membrane which includes the organic dye. A dye-sensitized solar cell comprises a first electrode, a second electrode which is formed on one side of the first electrode and includes a light absorptive layer, and electrolyte buried in a space between the first and second electrodes.
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Paragraph 0116; 0135-0140
(2018/02/10)
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- Synthesis of poly(thiophene-alt-pyrrole) from a difunctionalized thienylpyrrole by Kumada polycondensation
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A difunctional thienylpyrrole monomer with a bromide on the thienyl moiety and a magnesium halide on the pyrrole moiety was prepared via chemo-selective magnesium-iodine exchange. Based on this monomer, a π-conjugated alternating poly(thiophene-alt-pyrrole) PTP was synthesized via nickel and palladium catalyzed Kumada polycondensation. The optical and thermal properties of this polymer have been investigated and suggested a wide band gap polymer, with a very low Tg for such polymers.
- He, Lu-Ying,Urrego-Riveros, Sara,Gates, Paul J.,N?ther, Christian,Brinkmann, Maren,Abetz, Volker,Staubitz, Anne
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p. 5399 - 5406
(2015/07/15)
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- Nanostructured thermosets containing π-conjugated polymer nanophases: Morphology, dielectric and thermal conductive properties
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The nanostructured thermosets containing poly(3-hexylthiophene) (P3HT) nanophases were prepared by incorporating poly(ε-caprolactone)-block-poly(3-hexylthiophene)-block-poly(ε-caprolactone) (PCL-b-P3HT-b-PCL) triblock copolymer into epoxy. The PCL-b-P3HT-b-PCL triblock copolymer was synthesized via the combination of the polycondensation of 2-bromo-3-hexyl-5-iodothiophene and the ring-opening polymerization of ε-caprolactone; it was characterized by means of 1H nuclear magnetic resonance spectroscopy (1H NMR), gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). The morphologies of the nanostructured thermosets were investigated by means of transmission electron microscopy (TEM), small angle X-ray scattering (SAXS) and dynamic mechanical thermal analysis (DMTA). The results of small angle X-ray scattering (SAXS) showed that the P3HT nanophases were formed via self-assembly mechanism of the triblock copolymer in epoxy thermosets. Compared to control epoxy, the nanostructured thermosets containing the conjugated nanophases significantly displayed the enhanced dielectric constants. In the meantime, the thermal conductivity of the nanostructured thermosets was also enhanced and increased with increasing the content of P3HT nanophases.
- Li, Jingang,Cong, Houluo,Li, Lei,Zheng, Sixun
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p. 193 - 203
(2015/06/23)
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- Modulating crystallinity of poly(3-hexylthiophene) via microphase separation of poly(3-hexylthiophene)-polyisoprene block copolymers
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A series of poly(3-hexylthiophene)-block-polyisoprene (P3HT-b-PI) diblock copolymers (DBCP) and polyisoprene-block-poly(3-hexylthiophene)-block-polyisoprene (PI-b-P3HT-b-PI) triblock copolymers (TBCP) with accurately controlled molecular architecture were synthesized via highly efficient coupling reaction between aldehyde end-functionalized P3HT and living anionic polyisoprene. The self-assembly behaviors, considering morphology and crystallinity, of the thermal annealed bulk samples of these DBCPs and TBCPs containing various PI content were systematically investigated. The DBCPs behaved very differently from most published P3HT BCP systems, showing elongated fibers with preserved crystallinity regardless of the PI fraction. More noteworthy, with PI fraction less than 40 wt %, the DBCPs exhibited parallel straight fibers longer than several micrometers accompanied by concurrent enhanced crystallinity. The unique microstructure of the DBCPs might originate from moderate microphase separation between P3HT and PI as well as high flexibility of PI to conduct the packing of P3HT. The TBCPs, by contrast, exhibited highly curved interdomain boundaries with significant depressed crystallinity, resembling P3HT diblock copolymers in the strong phase segregation regime, as more pronounced entanglement of the two terminal PI segments would restrict the movement of P3HT.
- Lim, Herman,Chao, Chi-Yang,Su, Wei-Fang
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p. 3269 - 3281
(2015/06/08)
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- Influence of the bulkiness of the substituent on the aggregation and magnetic properties of poly(3-alkylthiophene)s
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A series of poly(3-alkylthiophene)s (P3ATs) (P1-P5) has been synthesized via a Ni(dppp)-mediated polymerization, varying the bulkiness of the alkyl side chains in order to investigate the influence of the bulkiness of the alkyl substituent on the aggregation and magnetic properties of P3ATs. UV-Vis spectroscopy, performed in solution as well as in film, shows that the stacking of the polymers becomes more complicated as the bulkiness of the side chains increases. Both the π-interactions and the planarization of the polymer chains are diminished. While aggregation is absent in poor solvent for the polymer with the most bulky side chains, aggregation was present in film, albeit slowed down. This behavior was also confirmed by X-ray diffraction (XRD) and differential scanning calorimetry (DSC) experiments. Electron spin resonance (ESR) measurements, performed at 300 K on powders, confirmed the trend of decreasing supramolecular order with increasing bulkiness of the side-chain. Magnetization measurements, performed at 5 and 300 K, are in line with our hypothesis on the influence of π-interactions and the fraction of planar polymer chains on the coercivity and saturation magnetization, respectively.
- Peeters, Helmuth,Jivanescu, Mihaela,Stesmans, Andre,Pereira, Lino M. C.,Dillemans, Leander,Locquet, Jean-Pierre,Van Bael, Margriet J.,Persoons, Andre,Koeckelberghs, Guy
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- Amphiphilic poly(3-hexylthiophene)-based semiconducting copolymers for printing of polyelectrolyte-gated organic field-effect transistors
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Polyelectrolytes are promising electronically insulating layers for low-voltage organic field effect transistors. However, the polyelectrolyte- semiconductor interface is difficult to manufacture due to challenges in wettability. We introduce an amphiphilic semiconducting copolymer which, when spread as a thin film, can change its surface from hydrophobic to hydrophilic upon exposure to water. This peculiar wettability is exploited in the fabrication of polyelectrolyte-gated field-effect transistors operating below 0.5 V. The prepared amphiphilic semiconducting copolymer is based on a hydrophobic regioregular poly(3-hexylthiophene) (P3HT) covalently linked to a hydrophilic poly(sulfonated)-based random block. Such a copolymer is obtained in a three-step strategy combining Grignard metathesis (GRIM), atom transfer radical polymerization (ATRP) processes, and a postmodification method. The structure of the diblock copolymer was characterized using FT-IR, 1H NMR spectroscopy, and gel permeation chromatography (GPC).
- Laiho, Ari,Nguyen, Ha Tran,Sinno, Hiam,Engquist, Isak,Berggren, Magnus,Dubois, Philippe,Coulembier, Olivier,Crispin, Xavier
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p. 4548 - 4557
(2013/07/11)
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- Dual selectivity: Electrophile and nucleophile selective cross-coupling reactions on a single aromatic substrate
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The development of a high yielding, both nucleophile and electrophile selective cross-coupling reaction with aromatic rings is presented. The reaction is general with respect to functional groups. Furthermore, the products still contain a boronic ester and a bromide. These two functional groups allow them to be easy-to-prepare, highly complex starting materials for further reactions, avoiding protecting group transformations.
- Heinrich, Annika C. J.,Thiedemann, Birk,Gates, Paul J.,Staubitz, Anne
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supporting information
p. 4666 - 4669
(2013/10/08)
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- A poly(3-hexylthiophene) block copolymer with macroscopically aligned hierarchical nanostructure induced by mechanical rubbing
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A highly ordered, uniformly aligned nanostructure with good crystallinity was first achieved on a P3HT block copolymer possessing a low weight fraction (19.4 wt%) of a flexible polyisoprene segment via a mechanical rubbing process without the use of solution based fabrication and thermal annealing. The attachment of the short polyisoprene segment to P3HT would significantly promote the main chain mobility to allow the orientation control of P3HT and of the self-assembled nanostructure by rubbing.
- Lim, Herman,Ho, Chun-Chi,Wu, Shang-Jung,Tsai, Hsin-Chieh,Su, Wei-Fang,Chao, Chi-Yang
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supporting information
p. 9146 - 9148
(2013/09/24)
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- Controlled synthesis of fullerene-attached poly(3-alkylthiophene)-based copolymers for rational morphological design in polymer photovoltaic devices
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Poly(3-alkylthiophene)-based diblock copolymers with controllable block lengths were synthesized by combining the Grignard metathesis method, Ni-catalyzed quasi-living polymerization, and a subsequent azide-alkyne click reaction to introduce a fullerene functionality into the side chains of one of the blocks. The fullerene-attached copolymers had good solubility (>30 g L-1 in chlorobenzene) with high molecular weights (Mn > 20 000). The diblock copolymer films formed clear nanostructures with sizes of ca. 20 nm, driven by crystallization of the poly(3-hexylthiophene) block and aggregation of the fullerene groups, as observed in AFM phase images. The copolymer-based photovoltaic device showed a power conversion efficiency of 2.5%, with a much higher fill factor of 0.63 in comparison to the previously reported single component devices. These results indicate that rational material designs enable the construction of suitable donor-acceptor nanostructures for photovoltaic applications, without relying on the mixing of materials.
- Miyanishi, Shoji,Zhang, Yue,Hashimoto, Kazuhito,Tajima, Keisuke
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p. 6424 - 6437
(2012/10/29)
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- AB block copoly(3-alkylthiophenes): Synthesis and chiroptical behavior
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In a first part of this article, the synthesis of AB type block copoly(3-alkylthiophene)s initiated by Ni(dppp)Cl2, the most commonly used initiator for these polymers, is investigated. For this study the respective 1H NMR resonances of all possible end-groups are identified. This result confirms the hypothesis that the Ni(dppp) species can walk back to the beginning of the polymer chain and that propagation can occur at both chain ends. The next part of the article studies the chiroptical behavior of AB-type block copoly(3-alkylthiophene)s with one chiral block and compares the results with those of the corresponding random copolymers. In order to obtain exclusively AB-type block copolymers, the polymers were prepared from a modified Ni initiator. They all have the same degree of polymerization but vary in the length of the respective blocks. The chiroptical behavior was studied by changing the ratio solvent/nonsolvent, meanwhile monitoring the UV-vis and circular dichroism (CD) spectra. Three series were investigated: one in which both blocks aggregate simultaneously, one in which the achiral block stacks before the chiral block, and one in which the chiral block stacks first followed by the achiral block. It was found that when the blocks stack independently, the (chiral/achiral) stacking of the latter is significantly influenced by the former. If both blocks of the polymer chains aggregate simultaneously, Cotton effects which are significantly larger than those of the chiral homopolymer are found.
- Verswyvel, Michiel,Monnaie, Frederic,Koeckelberghs, Guy
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scheme or table
p. 9489 - 9498
(2012/03/27)
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- Dye-functionalized head-to-tail coupled oligo(3-hexylthiophenes) - Perylene-oligothiophene dyads for photovoltaic applications
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A series of novel donor-acceptor systems, consisting of head-to-tail coupled oligo(3-hexylthiophene)s covalently linked to perylenemonoimide, is described. These hybrid molecules, which differ by the length of the oligothiophene units from a monothiophene up to an octathiophene, were created via effective palladium-catalyzed Negishi and Suzuki cross-coupling reactions in good to excellent yields. The optical and electrochemical properties of these compounds were determined and based on this series structure-property relationships have been established which give vital information for the fabrication of photovoltaic devices. Because the synthesized perylenyl-oligothiophenes distinguish themselves by a high absorption between 300 and 550 nm and an almost complete fluorescence quenching of the perylene acceptor, they meet the requirements for organic solar cells. The Royal Society of Chemistry 2005.
- Cremer, Jens,Mena-Osteritz, Elena,Pschierer, Neil G.,Muellen, Klaus,Baeuerle, Peter
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p. 985 - 995
(2007/10/03)
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- Chain-Growth Polymerization for Poly(3-hexylthiophene) with a Defined Molecular Weight and a Low Polydispersity
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The chain-growth polymerization for poly(3-hexylthiophene) (P3AT) with low polydispersity and defined molecular weight is studied. The Ni-catalyzed polymerizations of 3-alkyl-2-bromo-5-metalothiophene derivatives for HT-P3AT proceed via oxidative addition of the carbon-halogen linkage of polymer or monomer propagating end to the Ni catalyst. Two possible mechanisms accounting for the chain-growth nature of this polymerization were proposed. One is based on the difference in substituent effects between polymer and monomer propagating end while other is explained by the behavior of the active Ni catalyst.
- Yokoyama, Akihiro,Miyakoshi, Ryo,Yokozawa, Tsutomu
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p. 1169 - 1171
(2007/10/03)
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- New and efficient access to 3-substituted 2,5-dibromothiophenes. Consecutive nickel-catalyzed electrochemical conversion to thienylzinc species
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We have achieved the stepwise synthesis of 3-substituted thienylzinc reagents using both electrochemical methods and an original bromination procedure. For several compounds 3-bromothiophene was the starting substrate, which was functionalized according to recently developed electrochemical procedures. The nickel-catalyzed electrochemical reduction of the resulting 3-substituted 2,5-dibromothiophenes in the presence of zinc salts allowed the formation of monothienylzinc species in good yields. The selectivity of this reaction is discussed within the context of the electrochemical synthesis of regioregular polythiophenes.
- Mellah,Labbe,Nedelec,Perichon
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p. 318 - 321
(2007/10/03)
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- Regiocontrolled synthesis of poly(3-alkylthiophenes) mediated by Rieke zinc: Their characterization and solid-state properties
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A systematically regiocontrolled synthesis of poly(3-alkylthiophenes) (P3AT) mediated by Rieke zinc is reported. Rieke zinc undergoes oxidative addition to 2,5-dibromo-3-alkylthiophene or 2-bromo-5-iodo-3-alkylthiophene regioselectively to afford 2-bromo-5-(bromozincio)-3-alkylthiophene (2) or 2-bromo-5-(iodozincio)-3-alkylthiophene (10). The intermediate 2 or 10 can be polymerized catalytically to a series of regiospecific poly(3-alkylthiophenes) using different catalysts. The regioregularity of the polymer chain is solely controlled by the structure of the catalyst. An almost completely regioregular head-to-tail (HT) P3AT (4) is obtained by using Ni(DPPE)Cl2 ([1,2-bis-(diphenylphosphino)ethane]nickel(II) chloride). Use of Pd(DPPE)Cl2 leads to a reduction in the regioregularity (70: 30 HT/HH), while using Ni(PPh3)4 also leads to a much reduced regioregular P3AT (63:35 HT/HH). A totally regiorandom (50:50 HT/HH) P3AT (5) is afforded by using Pd(PPh3)4. The poly(3-butylthiophene) 4a is a 97% HT regioregular polymer. Other poly(3-alkylthiophenes) (alkyl = hexyl (4b), octyl (4c), decyl (4d), dodecyl (4e), and tetradecyl (4f)) are regioregular P3ATs with the HT linkage larger than 98.5% based on NMR analysis. Electronic absorption, X-ray diffraction, and crossed polarizing micrograph studies show that the cast films of the regioregular P3ATs (4) are self-organized, crystalline, flexible, and bronze-colored films with a metallic luster, while that of the regiorandom P3ATs (5) are amorphous and orange-colored films. The regioregular P3ATs exhibit a small bandgap (1.7 eV) which is 0.4 eV lower than that of regiorandom P3ATs (2.1 eV). Regioregular HT P3ATs have considerably improved electroconductivity and other physical properties over regiorandom P3ATs.
- Chen, Tian-An,Wu, Xiaoming,Rieke, Reuben D.
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p. 233 - 244
(2007/10/02)
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