Synthesis and properties of novel π-conjugated polymers by cycloaddition polymerization of bisthioketenes
双硫烯酮环加成聚合新型π-共轭聚合物的合成及性能
基本信息
- 批准号:12650865
- 负责人:
- 金额:$ 2.62万
- 依托单位:
- 依托单位国家:日本
- 项目类别:Grant-in-Aid for Scientific Research (C)
- 财政年份:2000
- 资助国家:日本
- 起止时间:2000 至 2001
- 项目状态:已结题
- 来源:
- 关键词:
项目摘要
π-Conjugated Polymers having electron-donating dithiafulvene units in the main chain were prepared by the cycloaddition reaction of aldothioketenes drived from p-conjugated diynes with their alkynthiol tautomers. These polymers formed soluble charge-transfer complexes with tetracyanoquinodimethane.π-Conjugated polymers having electron-donating dithiafulvene units and typical heteroaromatic (thiophene or pyridine) units in the main chain were prepared by the cycloaddition polymerization of aldothioketenes derived from heteroaromatic diynes (2,5-diethynylthiophene, 2,5-diethynyl-3-hexylthiophene and 2,5-diethynylpyridine) with their alkynethiol tautomers. The UV-vis absorption spectra of the polymers suggested that the p-conjugation systems in the polymers expanded more effectively than the polymer obtained from 1,4-diethynylbenzene reported previously. A redox active alternating π-conjugated copolymer of ferrocene with dithiafulvene was synthesized by cycloaddition polymerization of ald … More othioketene derived from 1,1'-bis(trimethylsilylethynyl)ferrocene The cyclic voltammogram of the polymer showed only one reversible potential due to effective interaction within the unit structure. A π-conjugated polymer containing a dithiafulvene unit and a bipyridyl unit was prepared by cycloaddition polymerization of aldothioketene derived from 5,5-diethynyl-2,2 -bipyridine. The UV-vis absorption spectra showed that the π-conjugation system of the polymer expanded more effectively than that of a benzene analogue of a poly(dithiafulvene) obtained from 1,4-diethynylbenzene. Cyclic voltammetry measurement indicated the dithiafulvene-bipyridyl polymer as a weaker electron donor polymer than the benzene analogue. These results agreed that the incorporation of the electron accepting bipyridyl moiety into the conjugated poly(dithiafulvene) induced an intramolecular charge-transfer (CT) effect between the units.We have prepared π-conjugated polymers with the 2,4-diylidene-l,3-dithietane unit by cycloaddition polymerization of bis(thioketene)s derived from bis(phosphonium salt)s. The electric properties of the polymers indicated that the polymers acted as strong electron donor than the poly(dithiafulvene)s. We have synthesized disilyl-substituted thiketene dimmers and demonstrated that effective s-p conjugations include the unique charge transfer from the thioketene dimmer to the Si-Si units, even though the Si-Si unit usually acts as an electron donor. Less
由对位共轭二炔衍生的醛硫烯酮与炔硫醇互变异构体进行环加成反应,制备了主链含给电子二硫富烯单元的π共轭聚合物。这些聚合物与四氰基醌二甲烷形成可溶性电荷转移络合物。通过由杂芳二炔(2,5-二乙炔基噻吩、2,5-二乙炔基-3-己基噻吩和2,5-二乙炔基吡啶)衍生的醛硫烯酮与它们的炔硫醇互变异构体的环加成聚合,制备了主链上含有给电子的二硫富烯单元和典型的杂芳(噻吩或吡啶)单元的π共轭聚合物。聚合物的紫外-可见吸收光谱表明,聚合物中的p-共轭体系比以前报道的由1,4-二乙炔基苯得到的聚合物更有效地扩展。采用ALD环加成聚合法合成了具有氧化还原活性的二茂铁-二硫富烯交替π共轭共聚物 ...更多信息 衍生自1,1 ′-双(三甲基甲硅烷基乙炔基)二茂铁的硫代烯酮由于单元结构内的有效相互作用,聚合物的循环伏安图仅显示一个可逆电势。以5,5-二乙炔基-2,2-联吡啶为原料,通过醛硫烯酮的环加成聚合,合成了一种含二硫富烯和联吡啶的π共轭聚合物。紫外-可见吸收光谱表明,该聚合物的π-共轭体系比由1,4-二乙炔基苯得到的聚二硫富烯的苯类似物的π-共轭体系更有效地扩展。循环伏安法测量表明,二硫富烯-联吡啶聚合物作为一个较弱的电子给体聚合物比苯类似物。这些结果表明,在共轭聚二硫富烯中引入受电子的联吡啶基团,在单元之间产生了分子内电荷转移(CT)效应。聚合物的电性能表明,该聚合物比聚二硫富烯具有更强的电子给体作用。我们已经合成了二甲硅烷基取代的硫乙烯酮二聚体,并证明有效的s-p共轭包括独特的电荷转移从硫乙烯酮二聚体的Si-Si单元,即使Si-Si单元通常作为电子供体。少
项目成果
期刊论文数量(22)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
K.Naka, T.Uemura, Y.Chujo: "π-Conjugated Poly(dithiafulvene)s and Poly(diselenafulvene)s : Effects of Side Alkyl Chains on Optical, Electrochemical and Conducting Properties"Macromolecules. (印刷中).
K.Naka、T.Uemura、Y.Chujo:“π-共轭聚(二硫富烯)和聚(二硒富烯):侧烷基链对光学、电化学和导电性能的影响”大分子(正在出版)。
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K.Naka, T.Uemura, Y.Chujo: "Alternating π-Conjugated Copolymer of Dithiafulvene with 2,2'-Bipyridyl Units"J. Polym. Sci., Polym. Chem.. 39・20. 3593-3603 (2001)
K.Naka、T.Uemura、Y.Chujo:“具有 2,2-联吡啶单元的二硫富烯的交替 π 共轭共聚物”J. Polym Sci.,Polym Chem. 39・20。 )
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Naka, K., Uemura, T., Chujo, Y.: "Electron Accepting System of Si-Si Bond in Linear Framework by Combination with Strong Donor"J. Am. Chem. Soc.. 123(25). 6209-6210 (2001)
Naka, K.、Uemura, T.、Chujo, Y.:“与强施主结合的线性骨架中Si-Si键的电子接受体系”J.
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T.Uemura, A.Gelover-Santiago, K.Naka, Y.Chujo: "Synthesis of a π-Conjugated Poly(thioketene dimer) and Its Electron Donating Property"Macromolecules. 34・3. 346-348 (2001)
T.Uemura、A.Gelover-Santiago、K.Naka、Y.Chujo:“π-共轭聚(硫烯酮二聚体)的合成及其给电子特性”34・3(2001)。
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S.Marathe, T.Uemura, K.Naka, Y.Chujo: "Synthesis and Properties of Oxygen, Methylene and Alkylene Bridged Poly(dithiafulvene)s"J. Polym. Sci., Polym. Chem.. 39・20. 3593-3603 (2001)
S.Marathe、T.Uemura、K.Naka、Y.Chujo:“氧、亚甲基和亚烷基桥接聚(二硫富烯)的合成和性能”J. 高分子化学。 39・20。 -3603 (2001)
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NAKA Kensuke其他文献
NAKA Kensuke的其他文献
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{{ truncateString('NAKA Kensuke', 18)}}的其他基金
Development of Functional Solid-state Materials having Molecular-Ordered Phase-Separated Nanostuructures by Designing of POSS-Core Dendrimers
通过 POSS 核心树枝状聚合物的设计开发具有分子有序相分离纳米结构的功能固态材料
- 批准号:
24350058 - 财政年份:2012
- 资助金额:
$ 2.62万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Construction of Polymers Containing Typical Elements Based on Radical Bismetallation of Acetyleneic Compounds
基于乙炔化合物自由基双金属化构建含典型元素的聚合物
- 批准号:
20350054 - 财政年份:2008
- 资助金额:
$ 2.62万 - 项目类别:
Grant-in-Aid for Scientific Research (B)
Synthesis and Functions of Metal Nanoparticle-Hybrids based on Cubic Silsesquioxanes
基于立方倍半硅氧烷的金属纳米颗粒杂化物的合成和功能
- 批准号:
16310086 - 财政年份:2004
- 资助金额:
$ 2.62万 - 项目类别:
Grant-in-Aid for Scientific Research (B)