Novel Synthesis of Electroresponsive Poly(thiophenylene) through a Michael-Type Addition

Yamamoto, Kimihisa; Higuchi, Masayoshi; Takai, Hirokazu; Nishiumi, Toyohiko

doi:10.1021/ol0068501

Cited by 11 publications

(3 citation statements)

References 21 publications

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“…However, due to insulating aliphatic Michael adducts, applications of the Michael addition to produce electronic organic materials have not been reported. 11 Recent interest has been stimulated by the potential use of organic radical molecules as an electronic and magnetic material. [12][13][14] We have synthesized a series of aliphatic polymers bearing pendant nitroxide radical groups and successfully utilized them as an electrode-active material for use in rechargeable devices.…”

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confidence: 99%

Nitroxide polymer networks formed by Michael addition: on site-cured electrode-active organic coating

et al. 2010

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Highly and homogeneously crosslinked poly(beta-ketoester) networks densely bearing robust nitroxide radicals were prepared via a click-type and stepwise Michael polyaddition. A half-battery cell composed of the thermally-cured radical network coatings displayed a rapid, reversible, and almost stoichiometric redox-activity even with a thickness of ca. 10 mum, which may be applicable as the electrode of organic-based rechargeable devices.

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confidence: 99%

Nitroxide polymer networks formed by Michael addition: on site-cured electrode-active organic coating

et al. 2010

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“…[ 11–16 ] However, the synthesis of poly(phenyl)sulfide derivatives is still a challenging task, which is usually achieved under drastic reaction conditions by radical reactions, [ 6,17–21 ] nucleophilic substitution of fluoroarenes [ 22–24 ] or via sulfonium cations. [ 18,25–28 ] Only recently transformations under milder reaction conditions were realized involving Michael‐type addition [ 29,30 ] or transition metal mediated carbon–sulfur bond forming reactions. [ 24,31,32 ] All of these transformations require the synthesis of thiophenol derivatives prior to the transition metal mediated reaction with the corresponding halo arene.…”

Section: Entrya) X Y Mnb) Mwb) Mw/mn Dpn Equiv 2 Mol% Cat G Mol−1 mentioning

confidence: 99%

Palladium‐Catalyzed Polycondensation for the Synthesis of Poly(Aryl)Sulfides

Hou

Oechsle

Kuckling

et al. 2020

Macromol. Rapid Commun.

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the sulfur atom in one transformation is the most desirable process, however, such a reaction is yet unprecedented. A solution to this shortcoming may be the use of hydrogen sulfide surrogates in CS cross couplings to access poly(phenyl)sulfide derivatives according to a polycondensation reaction. We and others have shown that silyl thiol, [35] thiourea [36] or potassium thioacetate [37] offer the unique access to diaryl sulfide derivatives. [36,[38][39][40][41][42] We here report the synthesis of poly(phenyl)sulfide and so far unprecedented poly(thiophene)sulfide through palladium catalyzed CS bond forming polycondensation.Poly (1,4-phenyl)sulfide is insoluble in organic solvents. Therefore, we turned our focus to alkyl-substituted phenylene derivatives to provide enhanced solubility with the aim to investigate the palladium catalyzed polycondensation reaction. 1,4-Dibromo-2,5-bis((2-ethylhexyl)oxy)benzene (1) was synthesized according to literature procedures [43] and was reacted with palladium(0) sources and hydrogen sulfide surrogates.From earlier studies in our group, we knew that the electron-rich [Pd(oTol 3 P) 2 ] complex in combination with the bis(diphenylphosphino)ferrocene ligand (dppf) performed best in the CS cross coupling to form diaryl sulfides. [38][39][40] Accordingly, we turned out attention to the optimization of the H 2 S-surrogate. Whereas thiourea [36] was inactive in the polycondensation, potassium thioacetate (KSAc, 2) was active in the conversion of 1 to polymeric material in the presence of 2 mol% Pd-catalyst (Table 1 entries 1-6). We identified impurities of the polymer after workup, which consisted according to 31 P NMR of phosphine and catalyst decomposition products. Attempted column chromatography did not lead to any improvement, so that we were not able to determine the yields of the reactions. However, NMR-spectroscopy, mass spectrometry and GPC analysis clearly show the synthesis of the poly(phenyl) sulfide polymer. The polymerization reactions displayed strong dependency on the ratio of 2 and the aryl halide. The optimum was determined to 0.94 equivalents (entry 2) as judged from the molecular weights. Such behavior is common for polycondensation reactions and optimization is required for new batches of coupling partners. Next, we studied the impact of catalyst loading on the polymerization. It was found that highest molecular weight was obtained in the presence of 10 mol% [Pd(oTol 3 P) 2 ]/dppf. However, the number average molecular weight (M n ) and the PDI were not dramatically affected by higher catalyst loadings (compare entries 2, 7 and 8 with 2, 4, and 10 mol%). Therefore, we decided to further optimize the reaction with 2 mol% of the palladium complex. Lithium salts The palladium-catalyzed CS cross coupling reaction is investigated as a novel efficient tool for the synthesis of poly(phenyl)sulfide derivatives. The reaction proceeds through the polycondensation of dibromo arenes with a H 2 S-surrogate to yield poly(aryl)sulfides. The reaction is generalized by the sy...

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“…Polyaniline is one of -conjugated polymers, [19][20][21][22][23][24][25][26] and can be regarded as Organic Polymers having Many Coordination Sites, which permit us to construct a reversible redox cycle for catalytic reactions. For example, polyanilines serve as catalysts in dehydrogenative oxidation under oxygen.…”

Section: Yamamoto Et Al Have Reported Syntheses Of Organic Polymers mentioning

confidence: 99%

Metal Ion Assembly in Macromolecules

Higuchi¹,

Hayashi²,

Kurth³

2006

J. Nanosci. Nanotech.

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Self-assembled organic-inorganic hybrid nano-materials have recently received much attention due to their novel and original functions, including new electronic, optical, magnetic, and catalytic properties. Especially, reactions in organic-metallic hybrid materials are closely related to biological reactions, such as the reactions in metal-containing protein, and the controlled metal ions assembly into organic polymers becomes very important. In the first part of this review, recent progresses in two types of organic-inorganic hybrid nano-materials (Organic compounds [character: see text] inorganic mesoporous materials and Metal ions [character: see text] organic polymer) are summarized. In the latter parts, dendrimer-metal complexes, examples of nature-mimetic materials, are introduced, and their controlled metal assembly in dendrimer and their application are reviewed.

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Novel Synthesis of Electroresponsive Poly(thiophenylene) through a Michael-Type Addition

Cited by 11 publications

References 21 publications

Nitroxide polymer networks formed by Michael addition: on site-cured electrode-active organic coating

Nitroxide polymer networks formed by Michael addition: on site-cured electrode-active organic coating

Palladium‐Catalyzed Polycondensation for the Synthesis of Poly(Aryl)Sulfides

Metal Ion Assembly in Macromolecules

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