Synthesis and Properties of One-Dimensional Conjugated Polymer (Carbyne).

研究了一维共轭聚乙烯醇的合成新方法。采用长时间掺杂fecl_3和聚偏氯乙烯合成立体特异性氯化聚乙炔（CHCl）_x的脱氢氯化策略。在使用DBU（1,8-重氮双环[5,4,0]十一-7-烯）作为强有机碱的脱氢氯化反应中，必须使用极性溶剂，如DMSO或DMF。紫外、可见光吸收、红外吸收和拉曼散射等光谱测量结果表明，脱氢氯化反应是通过HCl反式消去两步生成碳炔而非积云烯，生成的碳炔是由碳碳三键-(C C)_n （n = 10 ~ 40）的不同链长的聚乙烯段组成。同时也说明了这样合成的碳炔太不稳定，在空气和环境温度下，如果没有氧合和t三重键的交联，就不能存在。

Novel synthetic method of one-dimensional conjugated polyyne so-called carbyne is investigated. Synthetic strategy employed is dehydrochlorinations of stereospecifically chlorinated polyacetylene, (CHCl)_x which is synthesized through prolonged FeCl_3-doping and polyvinylidene chloride. In the dehydrochlorinations using DBU (1,8-diazabicyclo[5,4,0]undec-7-ene) as a strong organic base, usage of a polar solvent such as DMSO or DMF is essential. From spectroscopic measurements such as ultraviolet and visible absorption, infrared absorption, and Raman scattering, it is elucidated that the dehydrochlorination proceeds via two steps of trans elimination of HCl to yield carbyne but not cumulene, and that carbynes formed are composed of polyyne segments with various chain lengths of carbon-carbon triple bonding -(C C)_n-ranging n = 10 to 40. It is also elucidated that the carbyne thus synthesized is too labile to exist without an oxygenation and a cross-linking of the t riple bonds in air and at ambient temperature.