- Push-pull thiophene-based small molecules with donor and acceptor units of varying strength for photovoltaic application: Beyond P3HT and PCBM
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Here is reported an expedient synthesis implementing enabling technologies of a family of thiophene-based heptamers alternating electron donor (D) and acceptor (A) units in a D-A′-D-A-D-A′-D sequence. The nature of the peripheral A groups (benzothiadiazole vs. thienopyrrole-dione vs. thiophene-S,S-dioxide) and the strength of the donor units (alkyl vs. thioalkyl substituted thiophene ring) have been varied to finely tune the chemical-physical properties of the D-A oligomers, to affect the packing arrangement in the solid-state as well as to enhance the photovoltaic performances. The optoelectronic properties of all compounds have been studied by means of optical spectroscopy, electrochemistry, and density functional theory calculations. Electrochemical measurements and Kelvin probe force microscopy (KPFM) predicted a bifunctional behaviour for these oligomers, suggesting the possibility of using them as donor materials when blended with PCBM, and as acceptor materials when coupled with P3HT. Investigation of their photovoltaic properties confirmed this unusual characteristic, and it is shown that the performance can be tuned by the different substitution pattern. Furthermore, thanks to their ambivalent character, binary non-fullerene small-molecule organic solar cells with negligible values of HOMO and LUMO offsets were also fabricated, resulting in PCEs ranging between 2.54-3.96%. This journal is
- Boschi, Alex,Candini, Andrea,Di Maria, Francesca,Gazzano, Massimo,Lanzi, Massimiliano,Marinelli, Martina,Monti, Filippo,Pierini, Filippo,Salatelli, Elisabetta,Zanelli, Alberto,Zangoli, Mattia
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supporting information
p. 11216 - 11228
(2021/09/15)
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- Redox-Divergent Construction of (Dihydro)thiophenes with DMSO
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Thiophene-based rings are one of the most widely used building blocks for the synthesis of sulfur-containing molecules. Inspired by the redox diversity of these features in nature, we demonstrate herein a redox-divergent construction of dihydrothiophenes, thiophenes, and bromothiophenes from the respective readily available allylic alcohols, dimethyl sulfoxide (DMSO), and HBr. The redox-divergent selectivity could be manipulated mainly by controlling the dosage of DMSO and HBr. Mechanistic studies suggest that DMSO simultaneously acts as an oxidant and a sulfur donor. The synthetic potentials of the products as platform molecules were also demonstrated by various derivatizations, including the preparation of bioactive and functional molecules.
- Chen, Qing-An,He, Gu-Cheng,Hu, Yan-Cheng,Ji, Ding-Wei,Liu, Heng,Zhang, Xiang-Xin,Zhao, Chao-Yang
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supporting information
p. 24284 - 24291
(2021/10/08)
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- Planar and twisted molecular structure leads to the high brightness of semiconducting polymer nanoparticles for NIR-IIa fluorescence imaging
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Semiconducting polymer nanoparticles (SPNs) emitting in the second near-infrared window (NIR-II, 1000-1700 nm) are promising materials for deep-tissue optical imaging in mammals, but the brightness is far from satisfactory. Herein, we developed a molecular design strategy to boost the brightness of NIR-II SPNs: structure planarization and twisting. By integration of the strong absorption coefficient inherited from planar π-conjugated units and high solid-state quantum yield (φPL) from twisted motifs into one polymer, a rise in brightness was obtained. The resulting pNIR-4 with both twisted and planar structure displayed improved φPL and absorption when compared to the planar polymer pNIR-1 and the twisted polymer pNIR-2. Given the emission tail extending into the NIR-IIa region (1300-1400 nm) of the pNIR-4 nanoparticles, NIR-IIa fluorescence imaging of blood vessels with enhanced clarity was observed. Moreover, a pH-responsive poly(β-amino ester) made pNIR-4 specifically accumulate at tumor sites, allowing NIR-IIa fluorescence image-guided cancer precision resection. This study provides a molecular design strategy for developing highly bright fluorophores.
- Liu, Shunjie,Ou, Hanlin,Li, Yuanyuan,Zhang, Haoke,Liu, Junkai,Lu, Xuefeng,Kwok, Ryan T.K.,Lam, Jacky W.Y.,Ding, Dan,Tang, Ben Zhong
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supporting information
p. 15146 - 15156
(2020/10/13)
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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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- Single-material organic solar cells with fully conjugated electron-donor alkoxy-substituted bithiophene units and electron-acceptor benzothiadiazole moieties alternating in the main chain
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Main chain conjugated linear polymers, constituted by alternating electron-donor (D) and-acceptor (A) moieties, have been prepared with the aim of testing their performances as photoactive components in single material organic solar cells (SMOSCs). The D moiety is constituted by bithiophene co-units bearing in position 3 of the thiophene ring a hexyloxy, a hexyloxymethyl or a hexyl group, while the A moiety is represented by the benzothiadiazole group. The D-A polymers were obtained in high yield through the poorly demanding oxidative FeCl3 polymerization process-starting, respectively, from the related precursors 4,7-bis(3-hexyloxythiophen-2-yl)benzo[c][2,1,3]thiadiazole, 4,7-bis[3-(6-methoxyhexyl)thiophen-2-yl]benzo[c][2,1,3]thiadiazole and 4,7-bis(3-hexylthiophen-2-yl)benzo[c][2,1,3]thiadiazole-with low dispersity indexes, close to the monodisperse state, after fractionation with methanol. The materials have been thoroughly characterized for their physical and structural properties and then tested for photoconversion efficiency in SMOSCs by using different deposition procedures of the photoactive component. In agreement with Kelvin probe force microscopy (KPFM) measurements, the best photovoltaic performance was observed for the polymer based on conjugated 3-alkoxythiophene and benzothiadiazole moieties, achieving significant photocurrents for this type of fully conjugated alternating D-A structure (Jsc = 2.63-3.72 mA cm-2).
- Di Maria, Francesca,Lanzi, Massimiliano,Liscio, Andrea,Marinelli, Martina,Salatelli, Elisabetta,Zanelli, Alberto,Zangoli, Mattia
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supporting information
p. 4124 - 4132
(2020/04/15)
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- Synthesis of side-chain regioregular and main-chain alternating poly(bichalcogenophene)s and an ABC-type periodic poly(terchalcogenophene)
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Three unsymmetrical diiodobichalcogenophenes SSeI2, STeI2, and SeTeI2 and a diiodoterchalcogenophene SSeTeI2 were prepared. Grignard metathesis of SSeI2, STeI2, SeTeI2, and SSeTeI2 occurred regioselectively at the lighter chalcogenophene site because of its relatively lower electron density and less steric bulk. Nickel-catalyzed Kumada catalyst-transfer polycondensation of these Mg species provided a new class of side-chain regioregular and main-chain AB-type alternating poly(bichalcogenophene)s - PSSe, PSTe, and PSeTe - through a chain-growth mechanism. The ring-walking of the Ni catalyst from the lighter to the heavier chalcogenophene facilitated subsequent oxidative addition, thereby suppressing the possibility of chain-transfer or chain-termination. More significantly, the Ni catalyst could walk over the distance of three rings (ca. 1 nm) - from a thiophene unit via a selenophene unit to a tellurophene unit - to form PSSeTe, the first ABC-type regioregular and periodic poly(terchalcogenophene) comprising three different types of 3-hexylchalcogenophenes.
- Cheng, Kuang-Yi,Cheng, Yen-Ju,Huang, Sheng-Cih,Lai, Yu-Ying,Liang, Wei-Wei,Liu, Huai-Hsuan,Su, Yen-Chen,Yang, Hau-Ren
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p. 3836 - 3844
(2020/04/27)
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- Synthesis and Characterization of Diferrocenyl Conjugates: Varying π-Conjugated Bridging Ligands and its Consequence on Electrochemical Communication
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Organometallic wire-like complexes with ferrocenyl termini, conjugated with one and two units of thienylethynyl (M1 and M2) and thienyl (M3 and M4) groups, have been synthesized with a general formula of [Fc-C≡C-(Th-C≡C)1-2-Fc] and [Fc-(Th)1-2-Fc] (Fc = ferrocenyl, Th = thienyl) respectively. The diferrocenyl organometallic complexes have been characterized by various spectroscopic tools such as multinuclear NMR, FTIR, elemental analysis, and mass spectrometry. The electrochemical properties of these compounds have been investigated by cyclic (CV) and differential pulse voltammetry (DPV). The single reversible oxidation wave in diferrocenyl complexes with thienylethynyl spacers (M1 and M2) indicates the absence of intramolecular electrochemical communication between the two ferrocenyl termini. Interestingly, the diferrocenyl complexes with one and two thienyl spacers (M3 and M4) show two successive reversible one-electron oxidation waves, indicating electronic coupling between the two ferrocenyl (Fc) termini. The potential difference (ΔE1/2) between the two redox centers is 160 mV and 130 mV, respectively, with the corresponding comproportionation constants (Kc) of 6.2 × 102 and 1.5 × 102. Upon mono-oxidation of M3 by [Cp2Fe][BF4], a broad and weak intervalence charge-transfer (IVCT) transition is observed in the NIR region of 1200–2200 nm.
- Roy, Sourav Saha,Patra, Sanjib K.
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supporting information
p. 2193 - 2201
(2019/04/17)
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- Conductive triethylene glycol monomethyl ether substituted polythiophenes with high stability in the doped state
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Synthesis of two conducting polymers containing 3-hexylthiophene and 3-[2-(2-(2-methoxyethoxy)ethoxy)ethoxy]thiophene is demonstrated. In thin-film transistors, the high-molecular-weight polymer shows an average mobility of 4.2 × 10?4 cm2 V?1 s?1. Most importantly, the polymers have high conductivity upon doping with iodine and also have high stability in the doped state with high conductivities measured even after 1 month. Furthermore, the doping causes transparency to thin films of the polymer and the films are resistant to common organic solvents. All these properties indicate a great potential for the iodine-doped polymer to be used as an alternative to commercially available poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate).
- Dissanayake, Dushanthi S.,Gunathilake, Samodha S.,Udamulle Gedara, Chinthaka M.,Du, Jia,Yoo, Sang Ha,Lee, Youngmin,Wang, Qing,Gomez, Enrique D.,Biewer, Michael C.,Stefan, Mihaela C.
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p. 1079 - 1086
(2019/03/21)
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- ORGANIC SEMICONDUCTOR COMPOUND HAVING LOW BAND-GAP, AND TRANSISTOR AND ELECTRONIC DEVICE INCLUDING THE SAME
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Provided is an organic semiconductor compound comprising a structural unit represented by chemical formula (1). The definition of each substituent in chemical formula (1) is the same as that defined in the specification.(AA) Current density [mA/cm^2](BB) Voltage [V]COPYRIGHT KIPO 2018
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Paragraph 0178; 0184-0189
(2018/05/03)
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- Molecular engineering of face-on oriented dopant-free hole transporting material for perovskite solar cells with 19% PCE
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Through judicious molecular engineering, novel dopant-free star-shaped D-π-A type hole transporting materials coded KR355, KR321, and KR353 were systematically designed, synthesized and characterized. KR321 has been revealed to form a particular face-on organization on perovskite films favoring vertical charge carrier transport and for the first time, we show that this particular molecular stacking feature resulted in a power conversion efficiency over 19% in combination with mixed-perovskite (FAPbI3)0.85(MAPbBr3)0.15. The obtained 19% efficiency using a pristine hole transporting layer without any chemical additives or doping is the highest, establishing that the molecular engineering of a planar donor core, π-spacer and periphery acceptor leads to high mobility, and the design provides useful insight into the synthesis of next-generation HTMs for perovskite solar cells and optoelectronic applications.
- Rakstys, Kasparas,Paek, Sanghyun,Gao, Peng,Gratia, Paul,Marszalek, Tomasz,Grancini, Giulia,Cho, Kyung Taek,Genevicius, Kristijonas,Jankauskas, Vygintas,Pisula, Wojciech,Nazeeruddin, Mohammad Khaja
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supporting information
p. 7811 - 7815
(2017/07/13)
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- 'Donor-free' oligo(3-hexylthiophene) dyes for efficient dye-sensitized solar cells
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The common trend in designing dyes for use in DSSCs with iodide-based electrolyte is based on a donor-π spacer-acceptor (D-π-A) architecture. Here, we report two 'donor-free' cyanoacrylic end-functionalized oligo(3-hexylthiophene) dyes (5T and 6T). Despite having no donor group, both dyes show reversible first oxidation process. Both 5T and 6T have n-hexyl alkyl chains to retard aggregation at different positions as well as different numbers of thiophene moieties. However, the dyes showed similar absorption properties and redox potentials. The DSSCs based on these dyes give power conversion efficiencies of more than 7%, although a significant difference in the VOC and FF has been observed. Using electrochemical impedance spectroscopy, this is attributed to the presence of more trap states when 6T attaches to TiO2 and modifies the surface, mainly affecting the fill factor. Overall, these dyes introduce a new and effective design concept for liquid-electrolyte DSSC sensitisers.
- Hu, Yue,Ivaturi, Aruna,Planells, Miquel,Boldrini, Chiara L.,Biroli, Alessio Orbelli,Robertson, Neil
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supporting information
p. 2509 - 2516
(2016/02/20)
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- Conjugated Oligothiophene Derivatives Based on Bithiophene with Unsaturated Bonds as Building Blocks for Solution-Processed Bulk Heterojunction Organic Solar Cells
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A new building block ATVTA that uses stiff carbon–carbon triple bonds (A) on 1,2-di(2-thienyl)-ethene (TVT) has been developed. Oligothiophene derivatives S-01 with a TVT unit, S-02 with a 5,5′-diethynyl-2,2′-dithienyl (AT2) unit and S-03 with ATVTA were synthesized to compare their effects in a systematic study. Due to the better π-conjugation extension of the TVT unit, S-01 exhibits the most red-shifted absorption profile among them, whereas S-02 possesses the deepest HOMO level. While the HOMO level of S-03 is down-shifted by 0.02 eV relative to that of S-01, the alkyne linkages can effectively down-shift the HOMO level. By replacing the terminal units of S-03 with stronger electron acceptors, S-04 and S-05 exhibited broader absorption profiles and lower HOMO levels than those of S-03. Organic solar cells based on these molecules were fabricated and an S-03:PC60BM (1:1, w/w) based device afforded the highest Voc value of 0.96 V and a power conversion efficiency (PCE) of 2.19 %.
- Cui, Chaohua,Wu, Yue,Cheung, Man-Sing,Ho, Cheuk-Lam,Dong, Qingchen,Lin, Zhenyang,Li, Yongfang,Wong, Wai-Yeung
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p. 3557 - 3567
(2016/12/26)
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- Synthesis, characterization and performance of P3HT-azide-PCBM microgel
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Spherical Poly(3-hexylthiophene)-azide-[6,6]-phenyl-C61-butyric acid methyl ester (P3HT-azide-PCBM) microgel was synthesized by introducing an azide cross-linkable group into the conjugated polymer. Its UV-vis spectrum shifts blue as a result of the systematic disruption of planarity along the P3HT backbone and a reduction in long range conjugation. And the corresponding fluorescence spectrum also indicates that a strong intra-molecular photo-induced electron transfer is originated from the covalent linkage of PCBM moiety to the P3HT backbone via the hexyl bridge upon photo-excitation. Combined Gel Permeation Chromatography (GPC), dynamic and static light scattering (DLS and SLS) measurements prove that the resultant P3HT-azide-PCBM copolymer is a uniform spherical microgel with a hydrodynamic radius of 130 nm at room temperature. The spherical P3HT-azide-PCBM microgel can be used as electron donor or compatibilizer in bulk-heterojunction (BHJ) devices, but its introduction reduces the photovoltaic performance compared with the blend of P3HT/PCBM, because the hole mobility in the crosslinked polythiophene backbones is largely decreased.
- Wei, Guangmin,Li, Xinxin,Jia, Di,Cheng, He
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p. 5639 - 5645
(2016/07/06)
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- SUBSTITUTED NAPHTHYRIDINES AS ACCEPTOR MOLECULES FOR ELECTRONIC DEVICES
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The present invention provides the compounds of formula (1) wherein p is 1, 2, 3, 4, 5 or 6, and10 Ar1 is at each occurrence a 5 to 9 membered heteroaromatic moiety, which may be substituted with one or more substituents independently from each other selected from the group consisting of C1-20-alkyl, O-C1-20-alkyl, C(O)-C1-20-alkyl, C(O)-O-C1-20-alkyl, phenyl, F, Cl and Br, wherein C1-20-alkyl, C1-20-alkyl, O-C1-20-alkyl, C(O)-C1-20-alkyl and C(O)-O-C1-20-alkyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, Cl, Br and phenyl, wherein phenyl may be substituted with one or more substituents independently from each other selected from the group consisting of F, Cl, Br and C1-10-alkyl, and electronic devices comprising these compounds.
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Page/Page column 50
(2015/02/25)
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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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- 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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supporting information
p. 5399 - 5406
(2015/07/15)
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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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- Supramolecular engineering of oligothiophene nanorods without insulators: Hierarchical association of rosettes and photovoltaic properties
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Supramolecular rosettes of oligothiophenes that do not bear long aliphatic tails have been designed as semiconducting nanomaterials for solution-processable bulk het-erojunction solar cells. The rosettes consist of six barbiturat-ed thienyl[oligo(hexylthiophene)] units (Bar-T-hTn; n = 3,4,5) aggregated by multiple hydrogen bonds, which have been directly visualized by scanning tunneling microscopy (STM) at a solid-liquid interface. 1H NMR spectroscopy in [D8]toluene showed that Bar-T-hTn exists as a mixture of monomers and small hydrogen-bonded aggregates. Hierarchical organization of the hydrogen-bonded aggregates took place through π - π stacking interactions upon casting their toluene solutions, resulting in the growth of highly ordered nanorods whose widths are consistent with the diameters of the rosettes. The nanorods could be generated in the presence of soluble fullerene derivatives via solution casting or the annealing of the resulting thin films. The solar cells fabricated based on these bulk heterojunction films showed power conversion efficiencies of 1-3%, which are far higher than those of the non-hydrogen-bonded reference oligothiophene and the derivative that possesses long aliphatic tails.
- Yagai, Shiki,Suzuki, Mika,Lin, Xu,Gushiken, Marina,Noguchi, Takuya,Karatsu, Takashi,Kitamura, Akihide,Saeki, Akinori,Seki, Shu,Kikkawa, Yoshihiro,Tani, Yuki,Nakayama, Ken-Ichi
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supporting information
p. 16128 - 16137
(2015/02/19)
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- Structural design of benzo[1,2- b:4,5- b ′]dithiophene-based 2D conjugated polymers with bithienyl and terthienyl substituents toward photovoltaic applications
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In this contribution, six conjugated polymers consisting of benzo[1,2-b:4,5-b′]dithiophene-bithiophene (BDT-BT) and benzo[1,2-b:4,5-b′]dithiophene-benzothiadiazle (BDT-BTD) as building blocks in the main chain were synthesized by coupling polymerization and utilized for photovoltaic applications. By directly attaching three kinds of alkylthienyl side chains to the conjugated main chain, the resulted two-dimensional configuration revealed a broader absorption range due to the ground state electron transition of their corresponding alkylthienyl units and polymer backbone. Temperature-dependent absorbance, emission spectra, and thermal annealing further verify that the shoulder band(s) were originated from the aggregated (crystalline) species of polymers. The photovoltaic properties of the donor-acceptor polymers revealed well-defined side chain geometries, physical, and electronic structures and showed the highest power conversion efficiency of 4.25% among polymer solar cells based on two-dimensional (2-D) bithienyl- or terthienyl-substituted benzodithiophene.
- Kuo, Cheng-Yu,Nie, Wanyi,Tsai, Hsinhan,Yen, Hung-Ju,Mohite, Adytia D.,Gupta, Gautam,Dattelbaum, Andrew M.,William, Darrick J.,Cha, Kitty C.,Yang, Yang,Wang, Leeyih,Wang, Hsing-Lin
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p. 1008 - 1020
(2014/03/21)
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- Random poly(3-hexylthiophene-co-3-cyanothiophene) copolymers with high open-circuit voltage in organic solar cells
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Four novel random poly(3-hexylthiophene) copolymers containing 5-20% of 3-cyanothiophene are synthesized by Stille polycondensation; and their electrochemical, optical, charge transport, and photovoltaic properties are investigated. All polymers show high efficiencies and high open-circuit voltages (Voc) up to 0.81 V with a PC61BM acceptor in organic solar cells. Copyright
- Khlyabich, Petr P.,Rudenko, Andrey E.,Thompson, Barry C.
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p. 1055 - 1058
(2014/03/21)
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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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- Influence of the auxiliary acceptor on the absorption response and photovoltaic performance of dye-sensitized solar cells
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Three new dyes with a 2- (1,1-dicyanomethylene)rhodanine (IDR-I, -II, -III) electron acceptor as anchor were synthesized and applied to dye-sensitized solar cells. We varied the bridging molecule to fine tune the electronic and optical properties of the dyes. It was demonstrated that incorporation of auxiliary acceptors effectively increased the molar extinction coefficient and extended the absorption spectra to the near-infrared (NIR) region. Introduction of 2,1,3-benzothiadiazole (BTD) improved the performance by nearly 50%. The best performance of the dye-sensitized solar cells (DSSCs) based on IDR-II reached 8.53% (short-circuit current density (Jsc)=16.73 mAcm-2, open-circuit voltage (Voc)=0.71 V, fill factor (FF)= 71.26%) at AM 1.5 simulated sunlight. However, substitution of BTD with a group that featured the more strongly electron-withdrawing thiadiazolo [3,4- c]pyridine (PT) had a negative effect on the photovoltaic performance, in which IDR-III-based DSSCs showed the lowest efficiency of 4.02%. We speculate that the stronger auxiliary acceptor acts as an electron trap, which might result in fast combination or hamper the electron transfer from donor to acceptor. This inference was confirmed by electrical impedance analysis and theoretical computations. Theoretical analysis indicates that the LUMO of IDR-III is mainly localized at the central acceptor group owing to its strong electron-withdrawing character, which might in turn trap the electron or hamper the electron transfer from donor to acceptor, thereby finally decreasing the efficiency of electron injection into a TiO2 semiconductor. This result inspired us to select moderated auxiliary acceptors to improve the performance in our further study.
- Wu, Zhifang,Li, Xin,Li, Jing,Hua, Jianli,Agren, Hans,Tian, He
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p. 3549 - 3557
(2015/02/19)
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- Chloride surface terminated silicon nanocrystal mediated synthesis of poly(3-hexylthiophene)
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Abundant and environmentally benign metal-free silicon-based reagents, including chloride surface-terminated silicon nanocrystals (Cl-SiNCs) and silicon wafers as well as molecular chlorosilanes, were explored as catalysts for the synthesis of poly-3-hexy
- Islam, Muhammad Amirul,Purkait, Tapas K.,Veinot, Jonathan G. C.
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supporting information
p. 15130 - 15133
(2015/01/09)
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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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- "fibonacci's route" to regioregular oligo(3-hexylthiophene)s
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We describe a new synthetic approach to regioregular monodisperse oligo(3-alkylthiophene)s allowing for simple separation of regioregular material in gram quantities. The number of repeat units follows the Fibonacci numbers up to a length of 21. In a small adaption of this approach, introduction of a protecting group was used to synthesize an oligo(3-hexylthiophene) with 36 repeating units, the longest regioregular 3-hexylthiophene oligomer synthesized to date.
- Koch, Felix P. V.,Smith, Paul,Heeney, Martin
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supporting information
p. 13695 - 13698
(2013/10/01)
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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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- Transition between triangular and square tiling patterns in liquid-crystalline honeycombs formed by tetrathiophene-based bolaamphiphiles
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A series of 5,5′′′-diphenyl tetrathiophenes with polar glycerol groups at each end and two lateral flexible chains self-assemble into a series of liquid-crystalline honeycombs, formed by the π-conjugated rods which enclose polygonal prismatic cells filled by the lateral chains. With increasing chain length a discontinuous transition from triangular to square honeycombs takes place. At this transition a periodic honeycomb composed of a mixture of square and triangular cells in a ratio 1:2 was formed at low temperature, whereas at higher temperature a hexagonal columnar phase composed of triangular and randomly distributed rhombic cells, a new kind of cybotactic nematic phase, and also a cybotactic isotropic phase, both composed of square honeycomb fragments, represent the intermediate states. This provides an example of a dynamic self-assembled system where, depending on the molecular mobility, the transition between two periodic structures with different symmetry either leads to an increase of complexity, or to a chaotic regime with reduced order.
- Cheng, Xiaohong,Gao, Hongfei,Tan, Xiaoping,Yang, Xueyan,Prehm, Marko,Ebert, Helgard,Tschierske, Carsten
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p. 3317 - 3331
(2013/07/26)
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- Impact of molecular symmetry on single-molecule conductance
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We have measured the single-molecule conductance of a family of bithiophene derivatives terminated with methyl sulfide gold-binding linkers using a scanning tunneling microscope based break-junction technique. We find a broad distribution in the single-molecule conductance of bithiophene compared with that of a methyl sulfide terminated biphenyl. Using a combination of experiments and calculations, we show that this increased breadth in the conductance distribution is explained by the difference in 5-fold symmetry of thiophene rings as compared to the 6-fold symmetry of benzene rings. The reduced symmetry of thiophene rings results in a restriction on the torsion angle space available to these molecules when bound between two metal electrodes in a junction, causing each molecular junction to sample a different set of conformers in the conductance measurements. In contrast, the rotations of biphenyl are essentially unimpeded by junction binding, allowing each molecular junction to sample similar conformers. This work demonstrates that the conductance of bithiophene displays a strong dependence on the conformational fluctuations accessible within a given junction configuration, and that the symmetry of such small molecules can significantly influence their conductance behaviors.
- Dell, Emma J.,Capozzi, Brian,Dubay, Kateri H.,Berkelbach, Timothy C.,Moreno, Jose Ricardo,Reichman, David R.,Venkataraman, Latha,Campos, Luis M.
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supporting information
p. 11724 - 11727
(2013/09/02)
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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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- Electronic, redox and charge transport properties of an unusual hybrid structure: A bis(septithiophene) bridged by a fused tetrathiafulvalene (TTF)
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A hybrid tetrathiafulvalene-oligothiophene compound has been synthesised, in which the fulvalene unit is fused on both sides to an end-capped septithiophene oligomer. The compound (1) has been studied by cyclic voltammetry, UV-vis spectroelectrochemistry and X-ray crystallography. The properties of this material are compared to the half-unit (9), which lacks the TTF core and contains only one septithiophene chain. In the case of the larger molecule, there are multiple and complex redox processes leading to the loss of 6-8 electrons per molecule. Charge generation layer time-of-flight measurements give maximum hole mobilities of ca. 1 × 10-5 cm2 V-1 s-1.
- Wright, Iain A.,Skabara, Peter J.,Forgie, John C.,Kanibolotsky, Alexander L.,Gonzalez, Blanca,Coles, Simon J.,Gambino, Salvatore,Samuel, Ifor D. W.
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supporting information; experimental part
p. 1462 - 1469
(2011/09/30)
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- Synthesis and characterization of soluble low-bandgap oligothiophene-[all]- S,S-dioxides-based conjugated oligomers and polymers
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The synthesis and characterization of a new family of soluble oligothiophene-S,S-dioxides and their use as building blocks to form polythiophene-S,S-dioxides via microwave-assisted Stille coupling polymerization are described. Incorporation of the sulfone group into the polythiophene backbone leads to narrowing of the polymer bandgap, and while the energies of both Frontier orbitals in polythiophene-S,S-dioxide are lower with respect to polythiophenes, this tendency is considerably stronger for the lowest unoccupied molecular orbital than for the highest occupied molecular orbital, resulting in greater electron-accepting ability.
- Amir, Elizabeth,Sivanandan, Kulandaivelu,Cochran, Justin E.,Cowart, John J.,Ku, Sung-Yu,Seo, Jung Hwa,Chabinyc, Michael L.,Hawker, Craig J.
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scheme or table
p. 1933 - 1941
(2012/02/15)
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- Synthesis of a new conjugated polymer composed of pyrene and bithiophene units for organic solar cells
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An alternating conjugated copolymer composed of pyrene and bithiophene units, poly(DHBT-alt-PYR) has been synthesized. The synthesized polymer was found to exhibit good solution processibility and thermal stability, losing less than 5% of their weight on heating to approximately 370 °C. The synthesized polymer showed its maximum absorption and peak PL emission at 401 and 548 nm, respectively. The optical band gap energy of the polymer was determined by absorption onset to be 2.64 eV. Highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of the polymer was determined to be-5.48 and-2.84 eV by cyclic voltametry (CV) and the optical band gap. The polymer photovoltaic devices were fabricated with a typical sandwich structure of ITO/PEDOT:PSS/active layer/LiF/Al using poly(DHBT-alt-PYR) as an electron donor and C60-PCBM or C70-PCBM as electron acceptors. The open circuit voltage, short circuit current and fill factor of the device using C70-PCBM as an acceptor were 0.75 V, 3.80 mA/cm 2 and 0.28, respectively, and the maximum power conversion efficiency of the device was 0.80%. Copyright
- Lee, Sun-Young,Jung, Choong-Hwa,Kang, Jun,Kim, Hee-Joon,Shin, Won Suk,Yoon, Sung Cheol,Moon, Sang-Jin,Lee, Changjin,Hwang, Do-Hoon
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experimental part
p. 4367 - 4372
(2012/06/16)
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- Synthesis and electro-optical properties of fluorene-based copolymer for organic photovoltaic device application
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The following soluble π-conjugated polymer was synthesized by palladium-catalyzed Suzuki polymerization: poly[(9,9-dioctylfluorene)-alt-(3- hexylthiophen-5-yl)-(4'-hexylthiazol-5'-yl)] poly(FO-HThHTha) derived from poly(9,9-dioctylfluorene) (PFO) and poly[(3-hexylthiophen-5-yl)-2,2'-(4'- hexylthiazol-5'-yl)] poly(HThHTa). The polymer, poly(FO-HThHTa) was soluble in common organic solvents and easily spin coated onto indium-tin oxide (ITO) coated glass substrates. Bulk heterojunction photovoltaic cells with an ITO/PEDOT/poly(FO-HThHTa):PC70BM/TiOx/Al configuration were fabricated and the photovoltaic cell using poly(FO-HThHTa):PC 70BM (1:4) showed the best photovoltaic performance compared with those using poly(FO-HThHTa):PC70BM (1:2 and 1:6). The optimal bulk heterojunction photovoltaic cell exhibits a power conversion efficiency (PCE) of 0.39% (Voc=0.44 V, Jsc=2.57, FF = 0.34) with poly(FO-HThHTa):PC70BM (1:4) measured by using an AM 1.5G irradiation (100mW/cm2) on an Oriel Xenon solar simulator (Oriel 300W). Copyright Taylor & Francis Group, LLC.
- Kim, Jang Soo,Song, Myungkwan,Park, Jin Su,Yoon, Mikyoung,Yoon, Hoe Won,Kim, Ae Jin,Lee, Jae Wook,Gal, Yeong-Soon,Jin, Sung-Ho
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experimental part
p. 223 - 231
(2011/12/01)
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- A successful chemical strategy to induce oligothiophene self-assembly into fibers with tunable shape and function
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Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes into supramolecular crystalline fibers combining high charge mobility and intense fluorescence. The fibers were grown on various types of surfaces either as superhelices or straight rods depending on molecular structure. Helical fibers directly grown on a field effect transistor displayed efficient charge mobility and intrinsic 'memory effect'. Despite the fact that the oligomers did not have chirality centers, one type of hand-helicity was always predominant in helical fibers, due to the interplay of molecular atropisomerism and supramolecular helicity induced by terminal substituents. Finally, we found that the new sulfur overrich oligothiophenes can easily be prepared in high yields through ultrasound and microwave assistance in green conditions.
- Di Maria, Francesca,Olivelli, Pasquale,Gazzano, Massimo,Zanelli, Alberto,Biasiucci, Mariano,Gigli, Giuseppe,Gentili, Denis,D'Angelo, Pasquale,Cavallini, Massimiliano,Barbarella, Giovanna
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supporting information; experimental part
p. 8654 - 8661
(2011/07/29)
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- LiCl-promoted chain growth kumada catalyst-transfer polycondensation of the "reversed" thiophene monomer
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The effect of LiCl on the chain growth Kumada catalyst-transfer polycondensation (KCTP) of the "reversed" thiophene monomer, 5-bromo-2-chloromagnesio-3-hexylthiophene (3a) (that has bulky substituent adjacent to the chloromagnesium group), was investigate
- Wu, Shupeng,Huang, Li,Tian, Hongkun,Geng, Yanhou,Wang, Fosong
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scheme or table
p. 7558 - 7567
(2012/07/30)
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- ELECTRON DONATING ORGANIC MATERIAL, MATERIAL FOR PHOTOVOLTAIC ELEMENT, AND PHOTOVOLTAIC ELEMENT
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The invention aims at providing a photovoltaic device with high photoelectric conversion efficiency. The aim is attained by an electron donating organic material containing a benzothiadiazole compound in which (a) a benzothiadiazole skeleton and an oligothiophene skeleton are contained, (b) a band gap (Eg) is 1.8 eV or less, and (c) the level of the highest occupied molecular orbital (HOMO) is -4.8 eV or less, wherein said benzothiadiazole compound is formed by covalently combining the benzothiadiazole skeleton and the oligothiophene skeleton alternately, the proportion between the benzothiadiazole skeleton and the oligothiophene skeleton is within a range of 1:1 to 1:2 (however, excluding 1:1), and the number of thiophene rings contained in an oligothiophene skeleton is 3 or more and 12 or less.
- -
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Page/Page column 36-38
(2011/01/12)
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- Hypervalent iodine(III): selective and efficient single-electron-transfer (SET) oxidizing agent
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In 1994, we first determined the single-electron-transfer (SET) oxidation ability of phenyliodine(III) bis(trifluoroacetate) (PIFA) toward phenyl ethers, affording the corresponding aromatic cation radicals. Since then, hypervalent iodine(III) has been utilized as a selective and efficient SET oxidizing agent that enables a variety of direct C-H functionalizations of aromatic rings in electron-rich arenes under mild conditions. We have now extended the original method to work in a series of heteroaromatic compounds such as thiophenes, pyrroles, and indoles. The investigations and results obtained since the start of this century are summarized in this article.
- Dohi, Toshifumi,Ito, Motoki,Yamaoka, Nobutaka,Morimoto, Koji,Fujioka, Hiromichi,Kita, Yasuyuki
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experimental part
p. 10797 - 10815
(2010/03/01)
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- Mechanistic studies on Ni(dppe)Cl2-catalyzed chain-growth polymerizations: Evidence for rate-determining reductive elimination
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The mechanisms for Ni(dppe)Cl2-catalyzed chain-growth polymerization of 4-bromo-2,5-bis-(hexyloxy)phenylmagnesium chloride and 5-bromo-4-hexylthiophen-2-ylmagnesium chloride were investigated. Rate studies utilizing IR spectroscopy and gas chromatography revealed that both polymerizations exhibit a first-order dependence on the catalyst concentration but a zeroth-order dependence on the monomer concentration. 31P NMR spectroscopic studies of the reactive organometallic intermediates suggest that the resting states are unsymmetrical NiII-biaryl and Ni II-bithiophene complexes. In combination, the data implicate reductive elimination as the rate-determining step for both monomers. Additionally, LiCl was found to have no effect on the rate-determining step or molecular weight distribution in the arene polymerization.
- Lanni, Erica L.,McNeil, Anne J.
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supporting information; experimental part
p. 16573 - 16579
(2010/02/16)
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- Liquid-crystalline triangle honeycomb formed by a dithiophene-based X-shaped bolaamphiphile
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Soft supramolecular triangles: The molecule shown displays a new liquid-crystalline phase formed by a periodic array of triangular cylinders. The cylinders are fused to form a honeycomb by hydrogen-bonding networks running along the vertices, and the cells are filled by molten alkyl chains. The thickness of the walls separating the compartments is equal to the width of the π-conjugated rods.
- Cheng, Xiaohong,Dong, Xing,Wei, Guanghui,Prehm, Marko,Tschierske, Carsten
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supporting information; scheme or table
p. 8014 - 8017
(2010/02/27)
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- The influence of poly(3-hexylthiophene) regioregularity on fullerene-composite solar cell performance
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A comparison of three samples of poly(3-hexylthiophene) having regioregularities of 86, 90, and 96% is used to elucidate the effect of regioregularity on polymer-fullerene-composite solar cell performance. It is observed that polymer samples with lower regioregularity are capable of generating fullerene composites that exhibit superior thermal stability. The enhanced thermal stability of the composites is attributed to a lower driving force for polymer crystallization in the less regioregular polymer samples, which is supported with two-dimensional grazing incidence X-ray scattering and differential scanning calorimetry measurements. Furthermore, it is demonstrated that all three polymer samples are capable of generating solar cells with equivalent peak efficiencies of ～4% in blends with [6,6]-phenyl-C 61 -butyric acid methyl ester. While it may be non-intuitive that polymers with lower regioregularity can exhibit higher efficiencies, it is observed that the charge-carrier mobility of the three polymers is on the same order of magnitude (10-4 cm-2 V-1 s -1) when measured from the space-charge-limited current, suggesting that highly regioregular and crystalline polythiophenes are not required in order to effectively transport charges in polymer solar cells. Overall, these results suggest a design principle for semicrystalline conjugated polymers in fullerene-composite solar cells in which crystallization-driven phase separation can be dramatically suppressed via the introduction of a controlled amount of disorder into the polymer backbone.
- Woo, Claire H.,Thompson, Barry C.,Kim, Bumjoon J.,Toney, Michael F.,Frechet, Jean M. J.
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supporting information; experimental part
p. 16324 - 16329
(2009/05/09)
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- New amorphous semiconducting copolymers containing fluorene and thiophene moieties for organic thin-film transistors
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New amorphous semiconducting materials consisting of fluorene-based thiophene copolymers, poly(2-(5-(9,9-dibutyl-9 H-fluoren-2-yl)-3-hexylthiophen- 2-yl)-5-(3-hexylthiophen-2-yl)thieno[3,2-b]thiophene) P1 and poly(2-(5-(9,9-dibutyl-9 H-fluoren-2-yl)-4-hexylthiophen-2-yl)-5-(4- hexylthiophen-2-yl)thieno[3,2-b]thiophene) P2, have been successfully synthesized via a palladium-catalyzed Suzuki coupling reaction. The number-average molecular weights (Mn) of P1 and P2 were found to be 18300, and 15800, respectively. These polymers dissolve in common organic solvents such as chloroform, chlorobenzene, and toluene. The UV-vis absorption maxima of P1 and P2 appeared at 436 and 427 nm in solution and 441 and 431 nm in the film state, respectively. X-Ray diffraction (XRD) analysis showed no reflection peaks indicating amorphous collections of randomly oriented polymer chains. Atomic force microscopy (AFM) images of P1 and P2 showed amorphous film morphologies. Field-effect transistor mobilities of stable amorphous OTFTs of P1 and P2 under ambient conditions have been achieved up to 5.4 × 10 -4 cm2 V-1 s-1 and 1.6 × 10-4 cm2 V-1 s-1, respectively. The high stability and mobility of fluorene-based thiophene copolymers in the amorphous state make them a new family of promising candidates for organic thin-film transistors. The Royal Society of Chemistry.
- Park, Chan Eon,Kong, Hoyoul,Lee, Dong Hoon,Kang, In-Nam,Lim, Eunhee,Jung, Young Kwan,Park, Jong-Hwa,Ahn, Taek,Yi, Mi Hye,Shim, Hong-Ku
-
experimental part
p. 1895 - 1902
(2009/09/25)
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- Towards a general solid phase approach for the iterative synthesis of conjugated oligomers using a germanium based linker - First solid phase synthesis of an oligo-(triarylamine)
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The development of a germanium-based linker system for the solid phase synthesis (SPS) of 3-(n-hexyl)thiophene oligomers and the first SPS of triarylamine oligomers via iterative chain extension is described. The efficiency of the key steps in the oligomer syntheses and their compatibility with the germanium linker are demonstrated by the SPS of bi-[3-(n-hexyl) thiophene] 19 and ter-(triarylamine) 50. The use of a germanium-based linker in combination with appropriately selected silicon-based blocking/protecting groups allows double coupling to drive the key cross coupling steps to completion hence minimising deletion sequences and also allows for traceless and potentially functionalisative cleavage from the resin. The latter feature has yet to be fully explored but towards this end the first ipso-borodegermylation reaction of a 2-germyl-3-(n-hexyl)thiophene is presented. The Royal Society of Chemistry.
- Turner, David J.,Anemian, Remi,MacKie, Philip R.,Cupertino, Domenico C.,Yeates, Stephen G.,Turner, Michael L.,Spivey, Alan C.
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p. 1752 - 1763
(2008/02/10)
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- Preparation of regioregular alkylthiophene oligomers and their optical properties
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We successfully prepared regioregular hexylthiophene oligomers, dimmer to seximer of hexylthiophene, by using the Suzuki coupling. Introduction of hexyl chain provided excellent solubility to the oligothiophenes; even in seximer, the oligomer was soluble in conventional organic solvents such as toluene and chloroform. Additionally, the oligomer formed thin film with good uniformity by spin-coating from chloroform solution. In this article, we also report optical properties of the oligomer.
- Gondo, Schoichi,Goto, Yasuyuki,Era, Masanao
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p. 353 - 358
(2008/03/12)
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- Orientation and substituent effects on the properties of the diacetylene-group connected octaethylporphyrin-dihexylbithiophene derivatives (OEP-DHBTh-X) carrying electron-withdrawing groups
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Orientational isomers of the octaethylporphyrin-dihexylbithiophene (OEP-DHBTh) derivatives connected with a diacetylene linkage were synthesized, with various electron-withdrawing substituents X attached at the ends. The effects of DHBTh orientation and X substituent on the properties of OEP-DHBTh-X (X = H, Br, CN, CHO, and NO2) were studied and compared with those of related OEP derivatives.
- Hayashi, Naoto,Nishihara, Takashi,Matsukihira, Takuya,Nakashima, Hiroki,Miyabayashi, Keiko,Miyake, Mikio,Higuchi, Hiroyuki
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p. 371 - 386
(2008/02/11)
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- Enhancing the thermal stability of polythiophene:fullerene solar cells by decreasing effective polymer regioregularity
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Regioregularity has been shown to be an important aspect for the properties of poly(3-hexylthiophene) both in the pristine material and in bulk heterojunction photovoltaics with the fullerene derivative PCBM. Here we present a straightforward method to adjust the effective regioregularity of poly(3-hexylthiophene) by introducing 3,4-dihexylthiophene into the polymer chain. By investigating bulk heterojunction morphology and photovoltaic performance upon annealing, we observe that polythiophene with 91% regioregularity maintains equivalent electronic properties but forms a more thermally stable interpenetrating network with PCBM than polythiophene with regioregularity >96%. Copyright
- Sivula, Kevin,Luscombe, Christine K.,Thompson, Barry C.,Frechet, Jean M. J.
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p. 13988 - 13989
(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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- 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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- Synthesis and characterization of poly(triarylamine)s containing isothianaphthene moieties
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We report the synthesis, characterization, and properties of a new class of hole-transport dyes, poly(dithienylisothianaphthene phenyldiamine)s (poly-DTITNPDs). These polymers are characterized by the presence of a low band gap isothianaphthene (ITN) and triarylamine units in the main chain. A modified Ullmann polycondensation reaction using a phase-transfer catalyst was utilized to prepare these polymers. The optical, thermal, and electrochemical properties were studied and compared to those of poly(triphenyldiamine ether) without having an ITN group and poly(dithienylisothianaphthene) without having triarylamine groups in the main chain. The new polymers, reported here, exhibit improved thermal stability and higher glass-transition temperatures. The incorporation of ITN group into the main chain of a polytriarylamine causes an appreciable lowering of the band gap energy up to 1.6 eV. This results in light-harvesting hole-transport dyes having less mismatch with the solar spectrum. Moreover, these polymers exhibit reversible redox behavior and possess HOMO values of about -4.7 eV and LUMO values of about -2.9 eV.
- Kisselev, Roman,Thelakkat, Mukundan
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p. 8951 - 8958
(2007/10/03)
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