- Direct C–H Arylation as a Chemoselective Single-Step Access to π–Acceptor–π Type Building Blocks
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Different from the traditional multi-step synthesis, a chemoselective direct C–H arylation is reported for the single-step synthesis of various useful π–acceptor–π (π–A–π) type building blocks for use in organic electronics. This well-optimized C–H heteroarylation exhibits good product yields, broad substrate scope, and high functional group compatibility. Applications in the efficient synthesis of a new metal-free dye sensitizer for dye-sensitized solar cells (DSSCs) are also demonstrated. (Figure presented.).
- Lu, Kuan-Ming,Li, Wei-Ming,Lin, Po-Yu,Liu, Kuan-Ting,Liu, Ching-Yuan
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- Single precursor for the synthesis of donor and acceptor units of the low band gap polymers: Synthesis of benzodithiophene and thienopyrroledione from maleic anhydride
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An efficient route was developed to synthesize dimethyl thiophene-3,4-dicarboxylate from maleic anhydride. Dimethyl thiophene-3,4-dicarboxylate was used as a single precursor for synthesis of benzo[1,2-b:4,5-b′]dithiophene (BDT) and Thieno[3,4-c]pyrrole-4,6-dione (TPD) derivatives. BDT and TPD derivatives have been highly exploited as donor and acceptor units, respectively, to synthesize important donor-acceptor (D-A) conjugated polymers. BDT-based polymers were found to be one of the most efficient conjugated polymers for organic photovoltaic application. Synthesis of quinone precursor of the dihydroxybenzothiophene was accomplished by a new and unconventional methodology which includes reaction of 3,4-thiophene dicarboxylate with sodium hydride in THF. Dithienobenzoquinone dicarboxylate and dihydroxybenzodithiophene dicarboxylate were characterized structurally by single-crystal X-ray diffraction. Both compounds show strong π-stacking interaction and arrange in the parallel molecular sheets in the crystals.
- Kadam, Vinay S.,Patel, Arun L.,Zade, Sanjio S.
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p. 2608 - 2611
(2016/06/01)
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- Thieno[3,4-c]phosphole-4,6-dione: A Versatile Building Block for Phosphorus-Containing Functional π-Conjugated Systems
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A versatile phosphorus-containing π-conjugated building block, thieno[3,4-c]phosphole-4,6-dione (TPHODO), has been developed. The utility of this simple but hitherto unknown building block has been demonstrated by preparing novel functional organophosphorus compounds and bandgap-tunable conjugated polymers.
- Takeda, Youhei,Hatanaka, Kota,Nishida, Takuya,Minakata, Satoshi
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supporting information
p. 10360 - 10364
(2016/07/22)
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- Benzodithiophene and imide-based copolymers for photovoltaic applications
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Conjugated alternating copolymers were designed with low optical band gaps for organic photovoltaic (OPV) applications by considering quinoid resonance stabilization. Copolymers of thienoisoindoledione (TID) and benzodithiophene (BDT) had appreciably lower band gaps (by ~0.4 eV) than copolymers of thienopyrroledione (TPD) and BDT. In addition to intramolecular charge transfer stabilization (i.e., the "push-pull" effect), the former copolymer's quinoid resonance structure is stabilized by a gain in aromatic resonance energy in the isoindole unit. Additionally, the HOMO levels of the copolymers could be tuned with chemical modifications to the BDT monomer, resulting in open circuit voltages of greater than 1 V in photovoltaic devices. Despite the optimized band gap, TID containing polymers displayed lower photoconductance, as determined by time-resolved microwave conductivity, and decreased device efficiency (2.1% vs 4.8%) as compared with TPD analogues. These results were partially attributed to morphology, as computational modeling suggests TID copolymers have a twisted backbone, and X-ray diffraction data indicate the polymer films do not form ordered domains, whereas TPD copolymers are considerably more planar and are shown to form partially ordered domains.
- Braunecker, Wade A.,Owczarczyk, Zbyslaw R.,Garcia, Andres,Kopidakis, Nikos,Larsen, Ross E.,Hammond, Scott R.,Ginley, David S.,Olson, Dana C.
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experimental part
p. 1346 - 1356
(2012/08/28)
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- Acetic anhydride mediated condensation of aromatic o-diacid dichlorides with benzimidazoles to provide electro-reducible p-dione adducts
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Acetic anhydride mediates a facile and rapid condensation of benzimidazole with aromatic o-diacid dichlorides to precipitate p-dione adducts in excellent yields. Condensation with pyridine-3,4-dicarbonyl dichloride produced a 1:1 mixture of isomeric p-diones. The X-ray crystal structure of one of the latter isomers revealed unusual high density, and inter-layer separation similar to graphite. Cyclic voltammetry demonstrated that p-dione is capable of two consecutive one-electron-reductions with formal potentials influenced by the fused (hetero)aromatic and substituent effects.
- Joyce, Eamonn,Kavanagh, Paul,Leech, Dónal,Karpinska, Jolanta,McArdle, Patrick,Aldabbagh, Fawaz
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experimental part
p. 3788 - 3791
(2012/09/10)
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- Preparation and Characterisation of Thienonaphthoquinones and their Radical Ions
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Three naphthothiophene-4,9-diones (thienonaphthoquinones) have been prepared and their redox properties studied by chemical, electrochemical and EPR spectroscopic methods.All three quinones were readily reduced electrochemically to the corresponding radical anions and subsequently to dianions.The cyclic voltammograms showed evidence of ion pairing of the dianions.All three quinones were also electrochemically oxidised to radical cations.The structures and thermodynamic properties of the quinones, the radical cations, radical anions and dianions were studied by the semi-empirical AM1 method.The experimental redox potentials were found to correlate with the computed energies of the appropriate frontier MOs.The electrochemically generated radical anions were observed by EPR spectroscopy and shown to decay with second-order kinetics.The rate constants increased as the electron-releasing character of the substituents in the benzene ring increased.The only EPR spectroscopically detectable radical cation was that from the 6,7-dimethoxynaphthothiophene-4,9-dione.Attempts by electrochemical and chemical methods to polymerise the thienonaphthoquinones were unsuccessful.
- Crayston, Joe A.,Iraqi, Ahmed,Mallon, Philip,Walton, John C.
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p. 1589 - 1596
(2007/10/02)
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