116971-11-0Relevant articles and documents
Hierarchical helical assembly of conjugated poly(3-hexylthiophene)-block- poly(3-triethylene glycol thiophene) diblock copolymers
Lee, Eunji,Hammer, Brenton,Kim, Jung-Keun,Page, Zachariah,Emrick, Todd,Hayward, Ryan C.
, p. 10390 - 10393 (2011)
We report on the solution-state assembly of all-conjugated polythiophene diblock copolymers containing nonpolar (hexyl) and polar (triethylene glycol) side chains. The polar substituents provide a large contrast in solubility, enabling formation of stably suspended crystalline fibrils even under very poor solvent conditions for the poly(3-hexylthiophene) block. For appropriate block ratios, complexation of the triethylene glycol side chains with added potassium ions drives the formation of helical nanowires that further bundle into superhelical structures.
Synthesis and photovoltaic properties of polythiophene incorporating with 3,4-difluorothiophene units
Huang, Linquan,Yang, Dong,Gao, Qiang,Liu, Yan,Lu, Shengmei,Zhang, Jian,Li, Can
, p. 1385 - 1390 (2013)
Two polythiophene derivatives using fluorine atoms and hexyl or hexyloxy group as electron-withdrawing and donating substituents have been synthesized. The introduction of fluorine atoms to the polythiophene backbones simultaneously lowers the HOMO and narrows the bandgap, and the stronger electron-donating ability of hexyloxy side chain further reduces the bandgap. As a result, poly[3-hexylthiophene-2,5-diyl-alt-3,4-difluorothiophene] (PHTDFT) shows HOMO and bandgap of -5.31/1.83 eV and poly[3,4-dihexyloxythiophene-2,5-diyl-alt-3,4- difluorothiophene] (PDHOTDFT) shows HOMO and bandgap of -5.14/1.68 eV, both are lower than -4.76/2.02 eV of P3HT. Benefiting from the lower HOMO, PHTDFT:PC 61BM (1:1) polymer solar cells obtain a power conversion efficiency of 1.11% and an impressed open-circuit voltage of 0.79 V under solar illumination AM1.5 (100 mW/cm2). Two new polythiophene derivatives incorporating with 3,4-difluorothiphene units, PHTDFT and PDHOTDFT, show lower HOMO and narrower bandgap than that of P3HT. Benefiting from the lower HOMO, PHTDFT:PC61BM (1:1) polymer solar cells obtain a power conversion efficiency of 1.11% and an impressed open-circuit voltage of 0.79 V under solar illumination AM1.5 (100 mW/cm2). Copyright
Preparation of near-infrared absorbing composites comprised of conjugated macroligands on the surface of PbS nanoparticles
Zhang, Jinming,Bahrig, Lydia,Puetz, Andreas,Kanelidis, Ioannis,Lenkeit, Daniel,Pelz, Simon,Hickey, Stephen G.,Klein, Michael F.G.,Colsmann, Alexander,Lemmer, Uli,Eychmüller, Alexander,Holder, Elisabeth
, p. 5525 - 5533 (2013)
We report a facile macroligand strategy towards the synthesis of low-bandgap inorganic-organic composites comprised of semiconductor PbS nanoparticles and functional copolymers. For this, thiol-functional thiophene-based macroligands have been used as coligands for PbS nanoparticles. Thus, solution processable organic-inorganic hybrid materials with absorption in the near-infrared have been obtained. The resulting nanoparticle-polymer composites were characterized in detail by optical and FT-IR spectroscopy as well as TEM showing their potential as novel functional inorganic-organic hybrid materials when applied in initial proof-of-concept hybrid photovoltaic devices.
Controlling phase separation and optical properties in conjugated polymers through selenophene-thiophene copolymerization
Hollinger, Jon,Jahnke, Ashlee A.,Coombs, Neil,Seferos, Dwight S.
, p. 8546 - 8547 (2010)
Selenophene-thiophene block copolymers were synthesized and studied. The properties of these novel block copolymers are distinct from those of statistical copolymers prepared from the same monomers with a similar composition. Specifically, the block copolymers exhibit broad and red-shifted absorbance features and phase-separated domains in the solid state. Scanning transmission electron microscopy and topographic elemental mapping confirmed that the domains are either rich in selenophene or thiophene, indicating that the blocks of distinct heterocycles preferentially associate with one another in the solid state. This preference is surprising in view of the chemical similarities between repeat units. The overall results demonstrate a phase separation that is controlled by elemental differences. As a result of this phase separation, these novel conjugated block copolymers should find utility in a variety of studies and optoelectronics uses.
Copolymerization of Polythiophene and Sulfur to Improve the Electrochemical Performance in Lithium-Sulfur Batteries
Oschmann, Bernd,Park, Jungjin,Kim, Chunjoong,Char, Kookheon,Sung, Yung-Eun,Zentel, Rudolf
, p. 7011 - 7017 (2015)
We first report on the copolymerization of sulfur and allyl-terminated poly(3-hexylthiophene-2,5-diyl) (P3HT) derived by Grignard metathesis polymerization. This copolymerization is enabled by the conversion of sulfur radicals formed by thermolytic cleavage of S8 rings with allyl end-group. The formation of a C-S bond in the copolymer is characterized by a variety of methods, including NMR spectroscopy, size exclusion chromatography, and near-edge X-ray absorption fine spectroscopy. The S-P3HT copolymer is applied as an additive to sulfur as cathode material in lithium-sulfur batteries and compared to the use of a simple mixture of sulfur and P3HT, in which sulfur and P3HT were not covalently linked. While P3HT is incompatible with elementary sulfur, the new S-P3HT copolymer can be well dispersed in sulfur, at least on the sub-micrometer level. Sulfur batteries containing the S-P3HT copolymer exhibit an enhanced battery performance with respect to the cycling performance at 0.5C (799 mAh g-1 after 100 cycles for S-P3HT copolymer versus only 544 mAh g-1 for the simple mixture) and the C-rate performance. This is attributed to the attractive interaction between polysulfides and P3HT hindering the dissolution of polysulfides and the charge transfer (proven by electrochemical impedance spectroscopy) due to the homogeneous incorporation of P3HT into sulfur by covalently linking sulfur and P3HT.
Cross-linked conjugated polymer fibrils: Robust nanowires from functional polythiophene diblock copolymers
Hammer, Brenton A. G.,Bokel, Felicia A.,Hayward, Ryan C.,Emrick, Todd
, p. 4250 - 4256 (2011)
A series of poly(3-hexyl thiophene) (P3HT)-based diblock copolymers were prepared and examined in solution for their assembly into fibrils, and post-assembly cross-linking into robust nanowire structures. P3HT-b-poly(3-methanol thiophene) (P3MT), and P3HT-b-poly(3-aminopropyloxymethyl thiophene) (P3AmT) diblock copolymers were synthesized using Grignard metathesis (GRIM) polymerization. Fibrils formed from solution assembly of these copolymers are thus decorated with hydroxyl and amine functionality, and cross-linking is achieved by reaction of diisocyanates with the hydroxyl and amine groups. A variety of cross-linked structures, characterized by transmission electron microscopy (TEM), were produced by this method, including dense fibrillar sheets, fibril bundles, or predominately individual fibrils, depending on the chosen reaction conditions. In solution, the cross-linked fibrils maintained their characteristic vibronic structure in solvents that would normally disrupt (dissolve) the structures.
Approaching the Integer-Charge Transfer Regime in Molecularly Doped Oligothiophenes by Efficient Decarboxylative Cross-Coupling
Forgione, Pat,Hase, Hannes,Liu, Jiang Tian,Salzmann, Ingo,Taylor, Sarah
supporting information, p. 7146 - 7153 (2020/03/23)
A library of symmetrical linear oligothiophene was prepared employing decarboxylative cross-coupling reaction as the key transformation. Thiophene potassium carboxylate salts were used as cross-coupling partners without the need of co-catalyst, base, or additives. This method demonstrates complete chemoselectivity and is a comprehensive greener approach compared to the existing methods. The modularity of this approach is demonstrated with the preparation of discreet oligothiophenes with up to 10 thiophene repeat units. Symmetrical oligothiophenes are prototypical organic semiconductors where their molecular electrical doping as a function of the chain length can be assessed spectroscopically. An oligothiophene critical length for integer charge transfer was observed to be 10 thiophene units, highlighting the potential use of discrete oligothiophenes as doped conduction or injection layers in organic electronics applications.
