- Synthesis and Cyclization-Induced Charge Transfer of Rectangular Bisterthiophenesiloxanes
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Cyclization-modified terthiophene displays the change of emission behavior from locally excited (LE) to the intramolecular charge transfer (ICT) state. The rectangular bisterthiophenesiloxanes (DSiTh) was successfully prepared by π–π-stacking-aided hydrogen-bonding interactions. Cyclization-induced ICT in DSiTh could be observed, which was confirmed by absorption spectra, fluorescence spectra, and quantum chemistry analysis. The cyclization produces a strong intramolecular electron redistribution of a highly packed π-conjugated terthiophene. Thus, a distinctive variation of the dipole moment and a through-space ICT happen.
- Li, Chensen,Hu, Jian,Tashiro, Kohji,Ren, Zhongjie,Yan, Shouke
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- Synthesis and mesogenic properties of novel terthiophene derivatives
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To develop novel oligothiophene-based liquid crystals involving hydrogen bonding, new terthiophene derivatives containing a stearylamide group, N,N′-distearyl-5,5″-dicyano-2,2′:5′,2″- terthiophene-4,4″-dicarboxamide (DNC18DCN 3T) and N,N′-distearyl-5,5′-dipropyl-2,2′:5′, 2′-terthiophene-4,4″-dicarboxamide (DNC18 DP3T), were designed and synthesized, and their thermal behavior examined. Although DNC 18DP3T did not exhibit liquid crystallinity, DNC18DCN3T was found to form smectic A phase. Copyright Taylor & Francis Group, LLC.
- Liu, Ping,Liu, Miaomiao,Deng, Wenji
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- Solution-phase microwave-assisted synthesis of unsubstituted and modified α-quinque- and sexithiophenes
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The facile synthesis of poorly soluble unsubstituted and modified α-quinque- and sexithiophenes under microwave irradiation in the liquid phase is described. The use of microwave irradiation allowed these compounds to be prepared in a few minutes and at high yields by means of the Suzuki cross-coupling reaction. Unsubstituted sexithiophene was obtained in 10 min via the one-pot borylation/Suzuki reaction, purified according to a very simple procedure, and isolated in 84% yield. The efficient synthesis of two new methylated quinque- and sexithiophenes displaying liquid crystalline properties is reported. A new microwave-assisted methodology for the conversion of aldehyde-terminated quinque- and sexithiophenes into the corresponding cyano derivatives is also described. The use of microwaves was extended to the Sonogashira coupling reaction and found to be very effective in the preparation of a quinquethiophene containing acetylenic spacers. The electronic and optical characterization of this compound is reported and discussed in relation to that of unsubstituted quinquethiophene.
- Melucci,Barbarella,Zambianchi,Di Pietro,Bongini
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- Oligomerization of thiophene in the presence of PdCl42-
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In the presence of PdCl42- in alcohol/water solution, thiophene oligomerized to form α,α-coupled bithiophene while 2,2'-bithiophene oligomerized to form α,α-coupled tetrathiophene as the major products.In the case of thiophene, two unstable intermediates were isolated and characterized by 1H NMR as η1,C-bonded and η5,?-bonded thiophene-palladium(II) complexes.The mechanism of Α,α-coupling of is thus proposed.
- Wang, Dong-Liang,Hwang, Wen-Shu
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- Trisulfur radical anion as the key intermediate for the synthesis of thiophene via the interaction between elemental sulfur and NaO t Bu
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A facile base-promoted sulfur-centered radical generation mode and a single-step protocol for the synthesis of thiophene derivatives using 1,3-diynes via the interaction between elemental sulfur and NaOtBu has been reported. EPR experiments revealed that the trisulfur radical anion acts as a key intermediate of this process. A plausible mechanism has been proposed.
- Zhang, Guoting,Yi, Hong,Chen, Hong,Bian, Changliang,Liu, Chao,Lei, Aiwen
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- A new “naked-eye” colorimetric and ratiometric fluorescent sensor for imaging Hg2+ in living cells
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A new oligothiophene-based sensor 3 TH for monitoring Hg2+ has been designed and synthesized based on the intramolecular charge transfer (ICT) mechanism. The 3 TH shows the significant specificity toward Hg2+ through “naked-eye” colorimetric detection as well as via ratiometric fluorescence enhancement response with low detection limit of 62 nM. In addition, sensor 3 TH shows high selectivity and sensitivity for Hg2+ with fast response in a suitable pH range. Moreover, the 3 TH-based test strips was used to conveniently detect Hg2+ ions in water. Furthermore, considering its good ‘‘turn-on’’ fluorescent sensing behavior and low cell cytotoxicity, 3 TH was successfully applied to detect and image Hg2+ in real water samples and living cells, which shows great potentials for application in environmental and biological systems.
- Yin, Pengcheng,Niu, Qingfen,Yang, Qingxin,Lan, Linxin,Li, Tianduo
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- Influence of the molecular orientation of oligothiophene derivatives in vacuum-evaporated thin films on photovoltaic properties
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To understand the relationship between molecular orientation in organic thin films and organic photovoltaic properties the donor-acceptor type oligothiophene derivatives 5,5″-dicyano-2,2′:5′,2″- terthiophene and 5,5?-dicyano-2,2′:5′,2″:5″, 2?-quaterthiophene were synthesized. Polarizing optical microscopy showed that the oligothiophene derivatives had liquid crystalline properties. The crystalline phases of the oligothiophene derivatives showed molecular orientation. Atomic force microscopy also showed that the vacuum-evaporated oligothiophene derivative thin films had molecular orientation. Using the oligothiophene derivative thin films as donor materials and a 3,4,9,10-perylenetetracarboxylic dianhydride thin film as the acceptor material organic photovoltaic devices were fabricated. The structure of these devices is glass-indium tin oxide/donor materials/acceptor material/aluminum. The molecular orientation of the vacuum-evaporated oligothiophene derivative thin films was found to improve the organic photovoltaic performance of these devices.
- Hu, Jianhua,Liang, Lusheng,Chen, Tuhua,Liu, Ping,Deng, Wenji
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- Supramolecular formation of fibrous nanostructure in donor-acceptor dyad film
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A novel oligothiophene and its fullerene derivative were synthesized and their film morphologies were investigated. AFM images revealed that the oligothiophene formed well-aligned fiber-like nanostructures in the film after being thermally annealed at its liquid-crystalline temperature. In the oligothiophene-fullerene dyad film, fibers were already formed in the as-cast film. Thermal annealing further enhanced the structural order and a long, partially aligned fibrous nanostructure with a width of around 10 nm and a length of as long as 200 nm was observed. Combined with the results of X-ray analysis, these features were ascribed to supramolecular self-assembly via π-π interaction of the oligothiophene groups. Photovoltaic properties of the molecules were also investigated. The Royal Society of Chemistry.
- Nishizawa, Takeshi,Tajima, Keisuke,Hashimoto, Kazuhito
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- New oligothiophene-pentacene hybrids as highly stable and soluble organic semiconductors
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Two series of new oligothiophene-pentacene hybrid compounds were successfully synthesized and characterized, which consist of pentacene and anthradithiophene skeletons modified by different oligothienyl groups at 6,13 sites or 5,11 sites, respectively. Th
- Wang, Jing,Liu, Ke,Liu, Yi-Yang,Song, Cheng-Li,Shi, Zi-Fa,Peng, Jun-Biao,Zhang, Hao-Li,Cao, Xiao-Ping
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- Synthesis and antiproliferative activity of RITA and its analogs
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The synthesis of RITA and a variety of five-membered heterocyclic triads by the cyclocondensation of 1,4-bis(5-substituted-2-thienyl or 2-furyl)-1,3-butadiynes with water or Na2S·9H2O in the presence of KOH in DMSO is described. The study on the antiproliferative activities against K562, MCF-7, A549, and HCT116 tumor cells has revealed that some of the heterocyclic triads show higher antiproliferative activities than RITA, depending on the structures of substituents, the property of heteroatoms as well as their numbers.
- Jiang, Jianhua,Ding, Chao,Li, Lulu,Gao, Chunmei,Jiang, Yuyang,Tan, Chunyan,Hua, Ruimao
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- Using the nitro group to induce p-stacking in terthiophenes
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A new synthetic route to mononitrated oligothiophenes is described, as well as the preparation of halogenated derivatives (Br, I) thereof. An unusual deep red colour is observed and explained, with the aid of DFT calculations, as arising from a significant quinoidal contribution to the molecular structure. The crystal structures of two compounds, H(C4H2S) 3NO2 and Br(C4H2S) 3NO2, are presented. Both compounds have planar sheets held together by intermolecular short contacts (hydrogen bonds and, for the latter, NO2...Br interactions); the sheets do not directly superimpose, so the effect of the π-stacking is not maximized. Solid-state fluorescence and extended-Hueckel band-structure calculations are also presented for these materials.
- Sears, Wendy A.,MacKinnon, Craig D.,Mawhinney, Robert C.,Sinnemaki, Lauren C.,Johnson, Matthew J.,Winter, A. John,Robertson, Craig M.
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- THE SYNTHESIS OF ALPHA-THIOPHENE OLIGOMERS VIA ORGANOBORANES
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Oligomers containing from 2 to 6 thiophene units attached by their 2 and 5 positions were synthesized unambiguously by iodine oxidation of a suitable ate complex obtained by stepwise reactions of 9-BBN with methanol, a 2-lithiothiophene, boron trifluoride etherate, and a second 2-lithiothiophene.This is a one-pot procedure, carried out under nitrogen between -80 deg C and 0 deg C.
- Kagan, Jacques,Arora, Sudershan K.
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- Polythiophene Doping of the Cu-Based Metal-Organic Framework (MOF) HKUST-1 Using Innate MOF-Initiated Oxidative Polymerization
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The copper-based metal-organic framework (MOF) HKUST-1 adsorbs organic molecules into its pores. When loaded with electron-rich oligothiophenes, the resulting system reacts under heat to initiate oxidative polymerization without the use of any other oxidant or catalyst. This reaction is not observed in the non-redox-active MOF MIL-100(Al). We have characterized the composites by optical and nanoscale microscopy, vibrational and UV-vis spectroscopy, X-ray photoelectron spectroscopy, N2 sorption analysis, and thermogravimetric analysis/residual gas analysis. Unsubstituted oligothiophenes polymerize within MOF pores, while 3,4-ethylenedioxythiophene forms a coating on the MOF surface. MOF composites with conjugated polymer dopants trapped inside their pores undergo profound shifts in the composite electronic structure. Reasoning from time-dependent density functional theory calculations of an HKUST-1 model system bound to monomers, we rationalize the observed reactivity and propose an initiation mechanism based on a ligand-to-metal charge-transfer state.
- Marshall, Nicholas,James, William,Fulmer, Jeremy,Crittenden, Scott,Thompson, Anthony B.,Ward, Patrick A.,Rowe, Gerard T.
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- Novel protein kinase C inhibitors: α-terthiophene derivatives
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A series of α-terthiophene derivatives were prepared and their protein kinase C inhibitory activity were evaluated. The aldehyde derivatives were most potent inhibitors (IC50 1 μM). 2a-Terthiophene monoaldehyde was inactive in the inhibitions of protein kinase A, mitogen activated protein kinase and protein tyrosine kinase.
- Kim, Darrick S. H. L.,Ashendel, Curtis L.,Zhou, Qin,Chang, Ching-Te,Lee, Eung-Seok,Chang, Ching-Jer
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- Synthesis and liquid crystal properties of certain 5,5″-disubstituted 2,2′:5′,2″-terthienyls
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A preliminary account of the synthesis and liquid crystal properties of representative members of an homologous series of 5-alkanoyl-5″-alkyl-2,2′:5′,2″-terthienyls and the analogous 5,5″-di-alkyl-2,2′:5′,2″-terthienyls is given. The disposition of the three thiophene rings renders the molecular geometry sufficiently anisotropic that suitably substituted compounds are mesomorphic, and the liquid crystal transition temperatures of corresponding members of the two series are compared. The related 5,5′-disubstituted 2,2′-bithienyl derivatives are not mesomorphic.
- Byron,Matharu,Wilson,Wright
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- Wavelength-Dependent Singlet Oxygen Generation in Luminescent Lanthanide Complexes with a Pyridine-Bis(Carboxamide)-Terthiophene Sensitizer
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Lanthanide ion (LnIII) complexes, [Ln(3Tcbx)2]3+ (LnIII=YbIII, NdIII, ErIII) are isolated with a new pyridine-bis(carboxamide)-based ligand with a 2,2′:5′,2′′-terthiophene pendant (3TCbx), and their resulting photophysical properties are explored. Upon excitation of the complexes at 490 nm, only LnIII emission is observed with efficiencies of 0.29 % at 976 nm for LnIII=YbIII and 0.16 % at 1053 nm for LnIII=NdIII. ErIII emission is observed but weak. Upon excitation at 400 nm, concurrent 1O2 formation is seen, with efficiencies of 11 % for the YbIII and NdIII complexes and 13 % for the ErIII complex. Owing to the concurrent generation of 1O2, as expected, the efficiency of metal-centered emission decreases to 0.02 % for YbIII and 0.05 % for NdIII. The ability to control 1O2 generation through the excitation wavelength indicates that the incorporation of 2,2′:5′,2′′-terthiophene results in access to multiple sensitization pathways. These energy pathways are unraveled through transient absorption spectroscopy.
- Gracia-Nava, Manuel A.,Johnson, Katherine R.,Rack, Jeffrey J.,Vittardi, Sebastian B.,de Bettencourt-Dias, Ana
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- Preparation of extended di(4-pyridyl)thiophene oligomers
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Different methods for the coupling of 2-(4-pyridyl)thiophene to α-dibrominated thiophene oligomers and their efficiency to produce a homologous series of extended di(4-pyridyl)thiophene oligomers have been studied. The coupling was found to be most efficient with the organozinc derivative of 2-(4-pyridyl)thiophene, using a Pd(dppf) complex as the catalyst in the coupling reaction. The resulting compounds are promising new models for trans-membrane molecular conductors.
- Alberst, Willem M.,Canters, Gerard W.,Reedijk, Jan
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- Synthesis and liquid crystal properties of a novel family of oligothiophene derivatives
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In order to develop novel oligothiophene-based liquid crystals capable of hydrogen bonding, new terthiophene derivatives containing an alkylamide group, N,N′-dialkyl-5,5″-dichloro-2,2′:5′,2″- terthiophene-4,4″-dicarboxamide (DNCnDCl3T, n=8, 18)
- Liu, Ping,Zhang, Yamin,Feng, Guiju,Hu, Jianhua,Zhou, Xiaoping,Zhao, Qizhong,Xu, Yunhua,Tong, Zhen,Deng, Wenji
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- Solvent-free, microwave-assisted synthesis of thiophene oligomers via suzuki coupling
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The purpose of this study was to obtain a rapid, efficient, and environmentally friendly methodology for the synthesis of highly pure thiophene oligomers. The solvent-free, microwave-assisted coupling of thienyl boronic acids and esters with thienyl bromides, using aluminum oxide as the solid support, allowed us to rapidly check the reaction trends on changing times, temperature, catalyst, and base and easily optimize the experimental conditions to obtain the targeted product in fair amounts. This procedure offers a novel, general, and very rapid route to the preparation of soluble thiophene oligomers. Thus, for example, quaterthiophene was obtained in 6 min by reaction of 2-bromo-2,2′-bithiophene with bis(pinacolato)diboron (isolated yield 65%), whereas quinquethiophene was obtained in 11 min by reaction of dibremoterthiophene with thienylboronic acid (isolated yield 74%). The synthesis of new chiral 2,2′-bithiophenes is reported. The detailed analysis of the byproducts of some reactions allowed us to elucidate a few aspects of reaction mechanisms. While the use of microwaves proved to be very convenient for the coupling between conventional thienyl moieties, the same was not true for the coupling of thienyl rings to thienyl-S,S-dioxide moieties. Indeed, in this case, the targeted product was obtained in low yields because of the competitive, accelerated, Diels-Alder reaction that affords a variety of condensation products.
- Melucci, Manuela,Barbarella, Giovanna,Sotgiu, Giovanna
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- A colorimetric and fluorometric oligothiophene-indenedione-based sensor for rapid and highly sensitive detection of cyanide in real samples and bioimaging in living cells
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A new simple oligothiophene-indenedione-based sensor 3TI has been synthesized for the highly reactive and selective detection of cyanide anion (CN?) in 70% aqueous media. The sensor 3TI displays distinct colorimetric and fluorometric detection of CN? due to the addition of CN? to the electron-deficient indenedione-vinyl group of 3TI, which hampers intramolecular charge transfer (ICT) efficiencies. The recognition mechanism of 3TI for CN? was confirmed by the optical measurements, 1H NMR titration, FTIR spectra, HRMS analysis, and TD-DFT calculations. The sensor 3TI for CN? shows the outstanding advantages of high fluorescence brightness, fast response time (30 s), low detection limit (31.3 nM), minimal pH dependence in the physiologically relevant range, and excellent selectivity in presence of other competitive anions. Encouraged by these desirable sensing properties, the 3TI has been successfully used for determination of CN? in real water and food samples, silica-based sensing kits and fluorescence imaging in living cells with satisfactory results.
- Guo, Zongrang,Hu, Tingting,Sun, Tao,Li, Tianduo,Chi, Hong,Niu, Qingfen
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- Solution-processable tetrazine and oligothiophene based linear A-D-A small molecules: Synthesis, hierarchical structure and photovoltaic properties
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A series of high coplanar alternative linear small molecules with acceptor-donor-acceptor (A-D-A) structure containing electron-accepting tetrazine (Tz) moiety and electron-donating oligothiophenes (OTs) moiety, alkylated thiophene attached to both sides of the Tz moiety were designed and synthesized. The influences of varied oligothiophene length on small molecules' optical and electrochemical properties, crystallization, self assembling morphology in blend film with (6,6)-phenyl-C61-butyric acid methyl ester (PC61BM), and photovoltaic properties for the application as donor materials in organic solar cells (OSCs) were studied. The optical and electrochemical properties of small molecules showed that the HOMO and LUMO energy levels were determined by the number of OTs moiety and electron-accepting ability of Tz in the alternative small molecules, respectively. Meanwhile, the varied OT moieties can significantly affect the hierarchical structures when mixed with PC61BM. The molecule with intermediate conjugate moity length showed the highest ordering in its crystalline state, as revealed by differential scanning calorimetry (DSC) and X-ray diffraction experiments, and best photovoltaic properties when blended together with PC61BM or (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) as active layer in photovoltaic devices. The results indicate that hierarchical structures controlled by adjusting the conjugate moity length of small molecules is an effective way to improve the performance of OSCs. The photovoltaic device based on TT(HTTzHT)2:PC71BM with 1% DIO additives showed the best performance, with a Jsc of 7.87 mA/cm2 and a PCE of 3.24%.
- Chen, Yujin,Li, Chao,Zhang, Pan,Li, Yaowen,Yang, Xiaoming,Chen, Liwei,Tu, Yingfeng
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- Novel Electron Acceptors Bearing a Heteroquinonoid System. I. Synthesis and Conductive Complexes of 5,5'-Bis(dicyanomethylene)-5,5'-dihydro-Δ2,2'-bithiophene and Related Compounds
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Novel electron acceptors bearing a heteroquinonoid system, 5,5'-bis(dicyanomethylene)5,5'-dihydro-Δ2,2'-bithiophene, its 3,3'-dichloro, 3,3'-dibromo, and 3,3',4,4'-tetrabromo derivatives, and 5,5''-bis(dicyanomethylene)-5,5''-dihydro-Δ2,2':5',2''-tertiophene were synthesized by the action of tetracyanoethylene oxide or by Pd(0)-catalyzed substitution reactions with sodium dicyanomethanide on the corresponding α,α'-dihalogeno-heteroaromatics.They showed very small on-site Coulomb repulsion as expected, and afforded several highly conductive molecular complexes with electron donors such as hexamethylenetetratellurafulvalene.
- Yui, Koji,Aso, Yoshio,Otsubo, Tetsuo,Ogura, Fumio
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- Design, synthesis and biological evaluation of novel N-(4-([2,2′:5′,2″-Terthiophen]-5-yl)-2-methylbut-3-yn-2-yl) benzamide derivatives
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On the basis of the principle of combination of active groups, a series of novel N-(4-([2,2′:5′,2″-terthiophen]- 5-yl)-2-methylbut-3-yn-2-yl) benzamide derivatives were designed, synthesized and systematically evaluated for their antiviral activity agains
- Zhu, Youquan,Zhang, Haili,Wang, Danyang,Li, Lei,Xu, Han,Li, Huabin,Ma, Yuan
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- Synthesis and photovoltaic properties of donor-acceptor oligothiophene derivatives possessing mesogenic properties
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For the purpose of developing novel photovoltaic materials and organic photovoltaic devices with good performance characteristics, 5-cyano-2,2′: 5′,2″-terthiophene (3T-CN) and 5-cyano-2,2′:5′,2″: 5″,2″ ′-tetrathiophene (4T-CN) were synthesized. The 3T-CN and 4T-CN were donor-acceptor oligothiophene derivatives possessing mesogenic properties. The photovoltaic properties of 3T-CN and 4T-CN were studied. The rigid and flexible photovoltaic devices were fabricated using 3T-CN, 4T-CN, and 3,4,9,10-perylenetertracarboxylic dianhydride (PTCDA). The results showed that the -CN group played an important role in increasing short circuit current density (Isc) and power conversion efficiency (PCE). Both rigid device glass-ITO/4T-CN/PTCDA/Al and flexible device PET-ITO (indium tin oxides coated with polyethylene terephthalate)/4T-CN/PTCDA/Al had greater I sc and PCE compared with rigid device glass-ITO/4T/PTCDA/Al. It was possible that the -CN group, with strong electron-withdrawing character, and mesogenic properties of 4T-CN enhanced the efficiency by promoting forward interfacial electron transfer. Copyright Taylor & Francis Group, LLC.
- Guan, Li,Wang, Juan,Huang, Jiale,Jiang, Chuanyu,La, Ming,Liu, Ping,Deng, Wenji
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- Dicyanovinyl-substituted oligothiophenes: Structure-property relationships and application in vacuum-processed small molecule organic solar cells
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Efficient synthesis of a series of terminally dicyanovinyl (DCV)-substituted oligothiophenes, DCVnT 1-6, without solubilizing side chains synthesized via a novel convergent approach and their application as electron donors in vacuum-processed m-i-p-type planar and p-i-n-type bulk heterojunction organic solar cells is described. Purification of the products via gradient sublimation yields thermally highly stable organic semiconducting materials in single crystalline quality which allows for X-ray structure analysis. Important insights into the packing features and intermolecular interactions of these promising solar cell materials are provided. Optical absorption spectra and electrochemical properties of the oligomers are investigated and valuable structure-property relationships deduced. Photovoltaic devices incorporating DCVnTs 4-6 showed power conversion efficiencies up to 2.8% for planar and 5.2% for bulk heterojunction organic solar cells under full sun illumination (mismatch corrected simulated AM 1.5G sunlight). The 5.2% efficiency shown here represents one of the highest values ever reported for organic vacuum-deposited single heterojunction solar cells.
- Fitzner, Roland,Reinold, Egon,Mishra, Amaresh,Mena-Osteritz, Elena,Baeuerle, Peter,Ziehlke, Hannah,Koerner, Christian,Leo, Karl,Riede, Moritz,Weil, Matthias,Tsaryova, Olga,Weiss, Andre,Uhrich, Christian,Pfeiffer, Martin
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- Oligothiophene compounds inhibit the membrane fusion between H5N1 avian influenza virus and the endosome of host cell
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Hemagglutinin (HA) which is essential for influenza viral infection and replication has become a target for the design of anti-influenza drugs. A novel series of oligothiophene compounds focused on the target were synthesized as specific inhibitors agains
- Zhu, Zhibo,Liu, Shuwen,Yao, Zhili,Shen, Xiantian,Chen, Zhipeng,Liu, Xiangtao,Parquette, Jon R.,Liu, Shuwen
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- Synthesis and photovoltaic properties of formyl end-capped oligothiophenes
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For the purpose of developing novel photovoltaic materials, 5,5″-biformyl-2,2′:5′,2″-terthiophene (OHC-3T-CHO) and 5,5″-biformyl-2,2′:5′,2″:5″,2?:5?, 2″″-q-uinquethiophene (OHC-5T-CHO) were synthesized. The photovoltaic properties of OHC-3T-CHO and OHC-5T-CHO were studied. We have fabricated two flexible organic photovoltaic devices using OHC-3T-CHO, OHC-5T-CHO, and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA). The PET-ITO (indium tin oxides coated with polyethylene terephthalate)/OHC-3T-CHO/ PTCDA/Al device has an open circuit voltage (Voc) of 1.12V, and photoelectric conversion efficiency (PCE) of 1.00%, whereas the PET-ITO/OHC-5T-CHO/PTCDA/Al device has a Voc of 1.78V and PCE of 1.08%. Both devices have high Voc (1.12V and 1.78V). It is possible that intermolecular hydrogen bonding between the -CHO group of OHC-nT-CHO and the carboxylic dianhydride of PTCDA enhanced the efficiency by promoting forward interfacial electron transfer.
- Jiang, Chuanyu,Liu, Ping,Deng, Wenji
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- The synthesis and photoactivated cytotoxicity of novel 5-phenyl-3-(2, 2′:5′,2″-terthien-5-yl)-4,5-dihydro-1H-pyrazolines
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A series of novel 5-phenyl-3-(2,2′:5′,2′′-terthien- 5-yl)-4,5-dihydro-1H-pyrazolines were synthesized in this report. Their photoactivated cytotoxicities on the Spodoptera litura (SL) cell line were evaluated using the MTT method. It was noticed that the inhibitory activities of all the conjugates was enhanced when irradiated with UV-A light. Compounds 4, 6 and 8 were found to be most effective with inhibition rates of 88.1%, 88.0%, and 90.5%, respectively. For compound 5, the inhibition rate value was only slightly enhanced under the irradiation treatment (78.3%) compared to the dark treatment (74.8%). The relationship analysis between structure and activity showed that the middle thiophene ring played an important role on the inhibitory activities. It was shown that these compounds could be the potential candidates for new photoactivated pesticides.
- Luo, Zhi-Gang,Liu, Zheng-Yong,Yang, Zhuo-Hong
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- Synthesis, structure and cytotoxicity of trimethylsilyl oligothienylcarbaldehydes and their derivatives
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Trimethylsilyl end-capped bi- and terthiophene carbaldehydes were prepared by reaction of bi- and terthienyl lithium with DMF. Condensation of 5-trimethylsilyl-2,2′-bithiophene-5′-carbaldehyde with dinitrile of malonic acid gave silylbithienyl methylidenedinitrile in good yield, while reaction with hydroxylamine was accompanied by desilylation. The reaction of hydroxylamine with silylbithienyldinitrile leads to the formation of 2-[5-(5′-trimethylsilyl-2,2′-bithienyl)methylidene]malonic acid bisamidoxime. The cytotoxic effect of bi- and terthiophene derivatives was investigated in vitro on two monolayer tumor cell lines: MG-22A (mouse hepatoma) and HT-1080 (human fibrosarcoma). The molecular structure of 5-trimethylsilyl-2,2′-bithiophene-5′-carbaldehyde was studied by X-ray diffraction.
- Lukevics, Edmunds,Barbarella, Giovanna,Arsenyan, Pavel,Shestakova, Irina,Belyakov, Sergey,Popelis, Juris,Pudova, Olga
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- Novel low-bandgap oligothiophene-based donor-acceptor alternating conjugated copolymers: Synthesis, properties, and photovoltaic applications
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A series of novel soluble donor-acceptor lowbandgap-conjugated polymers consisting of different oligothiophene (OTh) coupled to electron-accepting moiety 2-pyran-4ylidenemalononitrile (PM)-based unit were synthesized by Stille or Suzuki coupling polymerization. The combination of electron-accepting PM building block with varied OThn (the number of thiophene unit increases from 3 to 5) results in enhanced π-π stacking in solid state and intramolecular charge transfer (ICT) transition, which lead to an extension of the absorption spectra of the copolymers. Cyclic voltammetry measurements and molecular orbital distribution calculations indicate that the highest occupied molecular orbitals (HOMO) energy levels could be fine-tuned by changing the number of thiophene units of the copolymers, and the resulting copolymers possessed relatively low HOMO energy levels promising good air stability and high-open circuit voltage (Voc) for photovoltaic application. Bulk heterojunction photovoltaic devices were fabricated by using the copolymers as donors and (6,6)phenyl C61-butyric acid methyl ester as acceptor. It was found that the highest Voc reached 0.94 V, and the short circuit currents (Jsc) were improved from 1.78 to 2.54 mA/cm2, though the power conversion efficiencies of the devices were measured between 0.61 and 0.99% under simulated AM 1.5 solar irradiation of 100 mW/cm 2, which indicated that this series copolymers can be promising candidates for the photovoltaic applications.
- Li, Yaowen,Li, Zaifang,Wang, Chunyu,Li, Hui,Lu, Hongguang,Xu, Bin,Tian, Wenjing
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- Cobalt-Catalyzed Glaser-type Homocoupling Reaction
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A highly efficient cobalt-catalyzed homocoupling of terminal alkynes with di-tert-butyldiaziridinone as the oxidant has been developed. The protocol tolerates a wide array of terminal alkynes, both activated and unactivated alkynes, to afford the corresponding conjugated 1,3-diynes. The mild reaction conditions further allow late-stage homocoupling of alkynes derived from complex natural products.
- Chen, Lin,Guo, Peng,Han, Jun-Fa,Ye, Ke-Yin
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- Electrochromic properties of pyrene conductive polymers modified by chemical polymerization
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Pyrene is composed of four benzene rings and has a unique planar melting ring structure. Pyrene is the smallest condensed polycyclic aromatic hydrocarbon, and its unique structural properties have been extensively studied. Pyrene has excellent properties such as thermal stability, high fluorescence quantum efficiency and high carrier mobility. This paper mainly used thiophene, EDOT and triphenylamine groups to enhance the pyrene based π-conjugated system and control the molecular accumulation of organic semiconductors, and improve their charge transport performances. Five kinds of polymer were synthesized and correspondingly characterized. The five kinds of pyrene conductive polymer had outstanding properties in terms of solubility, fluorescence intensity and thermal stability, good film-forming properties, stable electrochromic properties and high coloring efficiency. The coloration efficiency (CE) of PPYTP was as high as 277 cm2C?1, and the switching response time was short. The coloring time of PPYEDOT was 1.3 s and the bleaching time was 3.2 s. The lower impedance will also provide the possibility of such polymers being incorporated into electrochromic devices in the future. In short, the synthesized new pyrene conductive polymers will have wide application prospects in the field of electrochromic materials.
- Chang, Lijing,Hou, Yanjun,Li, Rui,Ma, Yang,Miao, Shoulei,Wang, Cheng,Xu, Haoran,Zhang, Yuhang
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p. 39291 - 39305
(2021/12/27)
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- Trithiocarbonate Anion as a Sulfur Source for the Synthesis of 2,5-Disubstituted Thiophenes and 2-Substituted Benzo[ b]thiophenes
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The trithiocarbonate anion (CS32-) was generated in situ from CS2 and KOH in dimethyl sulfoxide by a simple method and used as a novel synthetic equivalent of the S2- synthon for the synthesis of 2,5-disubstituted thiophenes from 1,3-butadiynes. Additionally, this system was employed for the metal-free synthesis of 2-substituted benzo[b]thiophenes from 2-haloalkynyl (hetero)arenes. These compounds were obtained from a cheap and readily available sulfur source in moderate to good yields, with good functional group tolerance.
- Paix?o, Douglas B.,Rampon, Daniel S.,Salles, Helena D.,Soares, Eduardo G. O.,Bilheri, Filipe N.,Schneider, Paulo H.
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supporting information
p. 12922 - 12934
(2020/11/26)
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- Approaching the Integer-Charge Transfer Regime in Molecularly Doped Oligothiophenes by Efficient Decarboxylative Cross-Coupling
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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.
- Forgione, Pat,Hase, Hannes,Liu, Jiang Tian,Salzmann, Ingo,Taylor, Sarah
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supporting information
p. 7146 - 7153
(2020/03/23)
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- Effect of a π-linker of push-pull D-π-A donor molecules on the performance of organic photodetectors
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We report organic photodetectors (OPDs) exhibiting high photocurrent density (Jph), low dark current density (Jd), and broadband external quantum efficiency (EQE) based on three push-pull type D-π-A small molecule donors (H1, H2, and H3) with different π-
- Chae, Sangmin,Choi, Min-Soo,Hong, Jong-In,Kim, Hyo Jung,Kim, Jang-Joo,Lim, Hong Chul
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p. 11145 - 11152
(2020/09/09)
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- Heterogeneous Nickel-Catalyzed Cross-Coupling between Aryl Chlorides and Alkyllithiums Using a Polystyrene-Cross-Linking Bisphosphine Ligand
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A polystyrene-cross-linking bisphosphine ligand PS-DPPBz was used for Ni-catalyzed cross-coupling with organolithiums. A bench-stable precatalyst [NiCl2(PS-DPPBz)] enabled efficient coupling reactions between aryl chlorides and alkyllithiums. The heterogeneous Ni system showed good reusability. (Figure presented.).
- Yamazaki, Yuki,Arima, Nozomi,Iwai, Tomohiro,Sawamura, Masaya
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p. 2250 - 2254
(2019/03/21)
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- Oligothienyl catenated germanes and silanes: Synthesis, structure, and properties
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The synthesis of two new groups of oligothienyl catenated silanes and germanes, Me5M2Thn (1a-b), Me5M2ThnM2Me5 (2a-c) (terminal), and ThnM2Me4Thn (3a-d) (internal) (M = Si, Ge; n = 2, 3; Th = 2- or 2,5-thienyl), is reported. The study of their structural parameters as well as of their spectral (NMR), electrochemical (CV) and optical (UV/vis absorbance, luminescence) properties has been performed in detail; in addition, the unexpected compound [Th2Si2Me4Th]2 (3a′) is also studied. Theoretical investigations have been performed for model compounds in order to establish structure-property relationships. The molecular structures of 2a (Me5Si2Th2Si2Me5), 2b (Me5Ge2Th2Ge2Me5), 3a (Th2Si2Me4Th2) and 3b (Th2Ge2Me4Th2) have been investigated by X-ray diffraction analysis. An effective conjugation with flattening of both Th planes in terminal 2a and 2b was observed. The main trends in the dependence of the optical and electrochemical properties on the structural parameters have been established. All of the compounds studied exhibit a strong emission within the 378-563 nm range, and the maximal quantum yield (up to 77%) is observed for the Si derivative 3a′. For the majority of the compounds, the quantum yields (20-30%) are significantly larger than for 2,2′-bi- and 2,2′:5′,5′′-terthiophenes. Due to their good emission properties, these compounds could be used to develop new materials with specific spectral properties.
- Zaitsev, Kirill V.,Lam, Kevin,Poleshchuk, Oleg Kh.,Kuz'Mina, Lyudmila G.,Churakov, Andrei V.
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supporting information
p. 5431 - 5444
(2018/04/23)
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- Donor-acceptor type fluorenyl nanometer grid material, preparation method and application thereof
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The invention discloses a donor-acceptor type fluorenyl nanometer grid material, a preparation method and application thereof. The nanometer grid material is of a square-ring-shaped rigid structure formed through alternative arrangement of fluorenyl ramification regarded as electron donor units and electron acceptor units. The preparation method comprises the following steps that a precursor with tertiary alcohol and aromatic nucleus terminal based hydrogen inhibitor dual binding sites is dissolved in organic solvent; at the room temperature, a catalyst is added, and stirring and reacting are conducted; and the reaction is conducted for 5 min-12 h, and products are obtained through chromatogram column separation. The donor-acceptor type fluorenyl nanometer grid material has the advantages that the compounding method is modularized, extensibility and stability of thermology, electrochemistry and photology are high; dependency of thin film solvent is reduced; large-area soluble processing is achieved; the size of apertures is accurately regulated and controlled; and accurate regulation an control of band gaps and energy level arrangement are achieved. The donor-acceptor type fluorenyl nanometer grid material has potential application prospects in the fields of photoelectric function materials of organic solar cells, storage and memory resistor, sensing, detecting and the like.
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Paragraph 0064; 0067
(2017/04/21)
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- A general approach to arylated furans, pyrroles, and thiophenes
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A general and practical synthetic method for aryl-substituted five-membered heterocycles has been developed. In the presence of KOH (30%), 1,4-diaryl-1,3-butadiynes undergo the cyclocondensation reaction with water, primary amines, and Na2S·9H2O in DMSO at 80 °C to afford 2,5-diarylfurans, 1,2,5-trisubstituted pyrroles, and 2,5-diarylthiophenes in good to high yields. Further studies have disclosed that aryl-substituted five-membered heterocycles can be also synthesized by a one-pot, two-step strategy from the terminal alkynes in DMSO firstly catalyzed by CuCl, and then via addition of KOH to promote the cyclocondensation of 1,3-butadiynes generated in situ.
- Zheng, Qingwei,Hua, Ruimao,Jiang, Jianhua,Zhang, Lei
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p. 8252 - 8256
(2015/03/05)
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- General suzuki coupling of heteroaryl bromides by using tri-tert-butylphosphine as a supporting ligand
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A general procedure for the fast Suzuki coupling of major families of heteroaryl bromides was realized by using Pd(OAc)2/PtBu3 as the catalyst. Many couplings were finished within minutes at room temperature in n-butanol. Different from previous studies, three typical heteroaryl bromides were systematically examined in couplings of various heteroaryl and aryl boronic acids. A fast, general coupling of heteroaryl bromides is realized by using a single palladium catalyst supported by tri-tert-butylphosphine.
- Zou, Yinjun,Yue, Guizhou,Xu, Jianwei,Zhou, Jianrong
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supporting information
p. 5901 - 5905
(2015/03/30)
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- Facilitated synthesis of functional oligothiophenes for application in thin film devices and live cell imaging
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This paper describes recent developments in the synthesis of ultrapure functional oligothiophene-based materials taking advantage of enabling techniques such as microwave/ultrasound irradiation and chitosan-supported palladium catalysts. Examples showing how ultrapure oligothiophenes self-organize in order to optimize charge transport in thin film devices and fluorescence emission inside living cells are reported.
- Dimaria, Francesca,Barbarella, Giovanna
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p. 627 - 637
(2014/01/06)
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- Sulfur heterocyclization and 1,3-migration of silicon in reaction of 1,3-diynes with sodium triisopropylsilanethiolate: One-pot synthesis of 2,5-disubstituted 3-(triisopropylsilyl)thiophenes
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Sulfur heterocyclization and 1,3-migration of silicon have been realized in the reactions of a range of 1,3-diynes with sodium triisopropylsilanethiolate in N,N-dimethylformamide. These provided 40-72% yields of 2,5-disubstituted 3-(triisopropylsilyl)thiophenes and up to 50% yield of 2,5-disubstituted thiophenes. Georg Thieme Verlag Stuttgart, New York.
- Tang, Jialiang,Ming, Ling,Zhao, Xiaoming
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p. 1713 - 1718
(2013/07/25)
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- Copper(I)-catalyzed synthesis of 2,5-disubstituted furans and thiophenes from haloalkynes or 1,3-diynes
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A regioselective synthesis of 2,5-disubstituted furans using copper(I) catalyst from haloalkynes in a one-pot procedure has been reported. This chemistry proceeds through the hydration reaction of 1,3-diynes, which can be readily prepared from the coupling reaction of haloalkynes in the presence of CuI. The procedure also can be used for the facile synthesis of 2,5-disubstituted thiophenes.
- Jiang, Huanfeng,Zeng, Wei,Li, Yibiao,Wu, Wanqing,Huang, Liangbing,Fu, Wei
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scheme or table
p. 5179 - 5183
(2012/07/03)
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- Polymer-supported syntheses of thiophene-containing compounds using a new type of traceless linker
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A new type of traceless linker is described for use in polymer-supported (PS) syntheses of thiophene-containing compounds. It is based on the cleavage of PS aryl 2-thienyl ketones by a mixture of potassium t-butoxide and water (typical mol ratio 10:3) in an ethereal solvent. Cleavage occurs to give the soluble thiophene-containing product. The method is used to prepare a range of eight thiophene-containing compounds including a terthiophene and a dialkylquaterthiophene. PS unsymmetrical diaryl ketones incorporating, for example, ortho-methoxyphenyl or pyrrole moieties could also serve as traceless linkers.
- Ben-Haida, Abderrazak,Hodge, Philip
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experimental part
p. 1754 - 1763
(2012/04/23)
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- Pseudo five-component synthesis of 2,5-di(hetero)arylthiophenes via a one-pot Sonogashira-Glaser cyclization sequence
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Based upon a consecutive one-pot Sonogashira-Glaser coupling-cyclization sequence a variety of 2,5-di(hetero)arylthiophenes were synthesized in moderate to good yields. A single Pd/Cu-catalyst system, without further catalyst addition, and easily available, stable starting materials were used, resulting in a concise and highly efficient route for the synthesis of the title compounds. This novel pseudo five-component synthesis starting from iodo(hetero)arenes is particularly suitable as a direct access to well-defined thiophene oligomers, which are of peculiar interest in materials science.
- Urselmann, Dominik,Antovic, Dragutin,Mueller, Thomas J. J.
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supporting information; experimental part
p. 1499 - 1503
(2011/12/22)
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- Synthesis of d-glucose and l-phenylalanine substituted phenylene-thiophene oligomers
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Phenylene-thiophene oligomers bearing peracetylated β-d-glucose or N-BOC-l-phenylalanine as chiral substituents were synthesized in good yields by a versatile protocol based on the Suzuki-Miyaura cross-coupling reaction. Aryl iodides bearing the chiral bi
- Hassan Omar, Omar,Babudri, Francesco,Farinola, Gianluca M.,Naso, Francesco,Operamolla, Alessandra,Pedone, Adriana
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experimental part
p. 486 - 494
(2011/03/18)
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- Oligothiophenes nano-organized on a cyclotetrasiloxane scaffold as a model of a silica-bound monolayer: Evidence for intramolecular excimer formation
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Excimer formation in a new class of terthiophene-based fluorophores covalently bonded to a cyclotetrasiloxane scaffold has been demonstrated and the photophysical process ruling it has been investigated in detail and modeled theoretically. In contrast to
- Mroz, Wojciech,Bombenger, Jean Philippe,Botta, Chiara,Biroli, Alessio Orbelli,Pizzotti, Maddalena,De Angelis, Filippo,Belpassi, Leonardo,Tubino, Riccardo,Meinardi, Francesco
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experimental part
p. 12791 - 12798
(2010/06/19)
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- 3D-conjugated systems based on oligothiophenes and phosphorus nodes
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3D-conjugated systems based on oligothiophene segments grafted on a phosphorus or on a phosphine oxide node have been synthesized. Under Stille coupling conditions, bromide terminated thienyl phosphine derivatives undergo a breaking of the phosphorus-carbon bond attributed to a ligand exchange with the Pd catalyst. The electronic properties of the new compounds have been analyzed by UV-vis and fluorescence spectroscopy and cyclic voltammetry.
- Leriche, Philippe,Aillerie, David,Roquet, Sophie,Allain, Magali,Cravino, Antonio,Frere, Pierre,Roncali, Jean
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body text
p. 3202 - 3207
(2009/02/03)
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- Process design and scale-up of the synthesis of 2,2′:5′,2′-terthienyl
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The objective of this study was the design of a scaleable process for the synthesis of 3-4 mol of α-terthienyl from 2,5-dibromothiophene and thienylmagnesium bromide in a 10-L stirred tank reactor. In THF the Grignard reagent, thienylmagnesium bromide, was readily formed from 2-bromothiophene and magnesium. To avoid crystallization the maximal concentration was limited to 1.4 M. Furthermore, the novel combination of THF and NiCl2[bis(diphenylphosphino)benzene] allows for fast double coupling of the Grignard reagent with 2,5-dibromothiophene. The concentration of catalyst could be limited to 0.5 mol % based on the amount of 2,5-dibromothiophene. An adapted workup procedure was developed, in which n-octane was used to separate the magnesium salts from the desired product. The reaction was performed in a (semi)batch-wise operated reactor. A global model for the coupling step proved to predict the results at 0.1-, 1-, and 10-L scales very accurately. The heat of reaction evolved in the coupling step was valorized and could be handled easily. Mixing of the feed stream and the reactor content proved to be another important factor in the scaling-up of the α-terthienyl synthesis.
- Smeets,Meijer,Meuldijk,Vekemans,Hulshof
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- Novel nucleoside analogues with fluorophores replacing the DNA base
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We describe the preparation and fluorescence properties of a set of new nucleosides in which a known hydrocarbon or oligothiophene fluorophore replaces the DNA base at C(1) of the deoxyribose moiety (see 3af). These compounds are potentially useful as pro
- Straessler, Christoph,Davis, Newton E.,Kool, Eric T.
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p. 2160 - 2171
(2007/10/03)
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- Synthesis of α-Thiophene Oligomers via Organotin Compounds
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A versatile synthetic route involving the use of organotin compounds has been applied for the preparation of functionalized oligothiophenes.Thus, substituted α-bithiophenes have been synthesized via the coupling reaction of 2-bromothiophenes with 2-trimethylstannylthiophene.The latter reagent couples with 2,5-dibromothiophenes to give the α-terthiophenes which are also accessible through the reaction of 5-trimethylstannyl-α-bithiophene with 2-bromothiophenes. 2,5-Bis(trimethylstannyl)thiophene and 5,5'-bis(trimethylstannyl)-α-bithiophene react with 2-bromothiophenes to give α-terthiophenes and α-quaterthiophenes, respectively. α-Quaterthiophene is also produced via the reaction of 5-trimethylstannylthiophene with 5,5'-dibromo-α-bithiophene.The coupling reaction of 5-trimethylstannyl-α-bithiophene with 2,5-dibromothiophene affords the α-quinquethiophene.The structures of the new compounds were confirmed by elemental analysis, Mass spectrometry, 1H- and 13C-NMR spectral data.Keywords: Functionalized α-thiophene oligomers; synthesis; 2-stannylthiophenes
- Kamal, Marwan R.,Al-Taweel, Samir A.,El-Abadelah, Mustafa M.,Ajaj, Khalid M. Abu
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- THE SYNTHESIS AND LIQUID CRYSTAL PROPERTIES OF CERTAIN 5,5''-DISUBSTITUTED 2,2':5',2''-TERTHIOPHENES
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The synthesis and liquid crystal properties of eight members of an homologous series of 5-n-alkanoyl-5''-n-alkyl-2,2':5',2''-terthienyls and the corresponding eight 5,5''-di-n-alkyl-2,2':5',2''-terthienyls are reported.The disposition of the three thiophene rings is sufficiently linear that suitably substituted compounds are mesomorphic, and the liquid crystal transition temperatures of related members of the two series are compared.Correasonding 5,5'-disubstituted 2,2'-bithienyls are not liquid crystalline.
- Byron, David,Matharu, Avtar,Wilson, Robert,Wright, Gavin
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- Inter- and Intramolecular Biaryl Couplings Via Cyanocuprate Intermediates
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Low temperature oxidations of selected higher order cyanocuprates composed of one or two heteroaromatic ligands can be oxidatively coupled in an inter- or intramolecular fashion to afford unsymmetrical biaryls.Non-heteroaromatic systems have also been studied in related intramolecular processes.
- Lipshutz, Bruce H.,Kayser, Frank,Maullin, Nathalie
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p. 815 - 818
(2007/10/02)
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