Polythiophene synthesis via halogen dance

Shono, Keisuke; Sumino, Yugo; Tanaka, Shota; Tamba, Shunsuke; Mori, Atsunori

doi:10.1039/c4qo00109e

Cited by 14 publications

(17 citation statements)

References 53 publications

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“…Scheme 1 Preparation of thiophene monomer 4a bearing benzenesulfonate group at the 3position Polymerization of the thus obtained chlorothiophenes 4a was carried out by the reaction with a bulky magnesium amide TMPMgCl•LiCl (2,2,6,6-teteramethylpiperidine-1-yl chloromagnesium: Knochel−Hauser base) 44 to undergo deprotonative metallation. [26][27][28][29][30][31][32][33][34][35] The addition of nickel catalyst 6 5 to the thus formed thiophene−magnesium species followed. Smooth polymerization took place at room temperature as shown in Scheme 2 to afford the corresponding polythiophene 6a in 66% yield as deep orange solid as shown in Scheme 2.…”

Section: Resultsmentioning

confidence: 99%

“…As shown in Scheme 4, the prepared monomer 4a was employed for statistical copolymerization with 2-chloro-3-hexylthiophene ( 11) with a nickel(II) catalyst. [26][27][28][29][30][31][32][33] Copolymerization of 4a and 11 was carried out using 1-20 mol % of 4a. A mixture of 4a and 11…”

Section: Synthesis and Characterization Of A Polyacetylene Derivativementioning

confidence: 99%

“…Accordingly, the introduction of HT-regioregularity into selfdoping polythiophenes is thereby a significant challenge in materials science. [13][14][15] (Fig 1 ) We considered synthesis of a water-soluble HT-regioregular poly-3-substituted thiophene, which posseses benzenesulfonic acid at the side chain employing deprotonative polymerization of 2-halo-3-substituted thiophene as a monomer precursor is employed [26][27][28][29][30][31][32][33] since we have, indeed, shown that synthesis of several side-chain functionalized polythiophenes have been prepared to date. 34,35 The acidic moiety should be protected during the polymerization employing an organometallic monomer and/or a transition metal catalyst.…”

Section: Introductionmentioning

confidence: 99%

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Thermally Induced Self-Doping of π-Conjugated Polymers Bearing a Pendant Neopentyl Sulfonate Group

et al. 2020

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Regioregular Head-to-tail (HT)-type polythiophene was synthesized by deprotonative nickel-catalyzed cross-coupling polymerization of 2-chlorothiophene bearing neopentyl benzenesulfonate group at the 3-position. The obtained HT-regioregular polymer was found dissolved in chloroform or THF, while it turned to water soluble upon heating the polymer 2 at 185 °C for 10 min by the liberation of the protected neopentyl group. The thin-film of the polymer showed remarkable improvement of the conductivity ca. 10 3 times before/after heating suggesting thermally-induced intramolecular doping polythiophene by the formed sulfonic acid at the side chain. The related doping was also observed in a poly(phenylacetylene) derivative, which was synthesized by rhodium-catalyzed polymerization. Copolymerization of such thiophene and acetylene bearing neopentyl sulfonate with 3-alkylthiophene and phenylacetylene produced the corresponding statistical copolymers, respectively, demonstrating the formal self-doping of poly(3-alkylthiophene) and poly(phenylacetylene).

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Section: Resultsmentioning

confidence: 99%

Section: Synthesis and Characterization Of A Polyacetylene Derivativementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermally Induced Self-Doping of π-Conjugated Polymers Bearing a Pendant Neopentyl Sulfonate Group

et al. 2020

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“…It was also shown that 2,5‐dibromothiophene 3 similarly afforded lithiated thiophene 2 (M=Li), and the thus formed 2 polymerized by the addition of nickel catalyst 19 , while the use of LDA (LiN i Pr 2 ) toward 3 induced deprotonation at the β‐position of the thiophene ring and halogen dance followed to afford α‐lithiated thiophene (Scheme ). The addition of nickel catalyst underwent polymerization to afford a new class of polythiophene bearing a carbon–bromine bond (halogen dance polymerization) …”

Section: Deprotonative Preparation Of the Monomer Species In Ht‐regiomentioning

confidence: 99%

Dehalogenative or Deprotonative? The Preparation Pathway to the Organometallic Monomer for Transition‐Metal‐Catalyzed Catalyst‐Transfer‐Type Polymerization of Thiophene Derivatives

Shibuya

Mori

2020

Chemistry A European J

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Due to a wide range of applications in electronic materials, polythiophenes attract considerable attention in organic and polymer syntheses as well as in materials science. For the purpose of developing the practical synthetic protocol, this review focuses on the deprotonative pathway in the preparation of thiophene organometallic monomer, which was shown to be effective employing 2‐halo‐3‐substituted thiophene as a monomer precursor. The thus metallated thiophene monomer was shown to undergo polymerization by nickel(II) complex catalysis, with which highly regioregular head‐to‐tail (HT)‐type polythiophenes were obtained with controlled molecular weight and molecular weight distribution. Several polythiophene derivatives with modified thiophene‐ring and side‐chain structures were shown to be designed in order to achieve the designed functionality as materials.

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“…17 Treatment of the polymer in THF under reflux for 1 day formed the debrominated product as shown in Scheme 5(a). Reductive transformation of (3T-Br) n proceeded with tBuMgCl as a reducing agent in the presence of NiCl 2 dppf as a catalyst.…”

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confidence: 99%

Linear-selective cross-coupling polymerization of branched oligothiophene by deprotonative metalation and cross-coupling

2015

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Brominated oligothiophene with a branched structure was subjected to deprotonative metalation with a bulky magnesium amide chloromagnesium 2,2,6,6-tetramethylpiperidine-2-yl lithium chloride salt (TMPMgCl·LiCl), which is known as the Knochel-Hauser base. The thus metalated oligothiophene was polymerized in the presence of a nickel(II) NHC (N-heterocyclic carbene) complex to afford polymers of M n of 4400 to 44 000, which corresponds well with the monomer feed/catalyst loading ratio. Analysis by MALDI-TOF MS suggests the formation of a linear polymer with oligothiophene as the monomer. Polymerization of 7-mer (7T-Br 4 ) also affords polythiophene of a similar structure.Chart 1 Oligothiophene dendrimers. † Electronic supplementary information (ESI) available: Synthetic procedures and characterisation data. See

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Polythiophene synthesis via halogen dance

Abstract: Polymerization of thiophene with a Ni(ii) catalyst through halogen dance leads to a new class of polythiophenes.

Cited by 14 publications

References 53 publications

Thermally Induced Self-Doping of π-Conjugated Polymers Bearing a Pendant Neopentyl Sulfonate Group

Thermally Induced Self-Doping of π-Conjugated Polymers Bearing a Pendant Neopentyl Sulfonate Group

Dehalogenative or Deprotonative? The Preparation Pathway to the Organometallic Monomer for Transition‐Metal‐Catalyzed Catalyst‐Transfer‐Type Polymerization of Thiophene Derivatives

Linear-selective cross-coupling polymerization of branched oligothiophene by deprotonative metalation and cross-coupling

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