A Novel Synthesis of Polymers with Dimensionally Extended pi-Conjugation by Solid-State Polymerization and Their Physical Properties

合成了一些四烷和己烷衍生物，然后用伽马射线在固态中进行了聚合。得到的π共轭聚合物看起来像金属。具有氨基甲酸乙酯基团的四烷化合物是最易聚合的。具有芳基的类似化合物给出了足够大的晶体用于x射线单晶结构测定，从而确定了聚合物结构，即直接结合二乙炔的聚二乙炔。然而，很明显，二乙基部分与阶梯聚合物的反应并不容易进行。激子引起的紫外吸收峰随着π共轭的扩展发生了色移，其位移程度与侧链上乙炔基团的数目成正比。chi^<(3)>的值为ca.10^<-9> esu，比普通聚二乙酰基提高了约一个数量级。

Some tetrayne and hexayne derivates were synthesized and then polymerized in the solid-state by gamma-ray. The resulting pi-conjugated polymers looked like metal. The tetrayne compounds with urethane groups were the most polymerizable. The similar compounds having aryl groups gave large enough crystals for X-ray single crystal structure determination, resulting in the confirmation of the polymer structure, i.e. a polydiacetylene with directly bound diacetylenic moiety. However, it has become apparent that the reaction of diacethlenic moiety to ladder polymer does not proceed so easily. UV absorption peaks due to exciton were shifted bathochromically with extending pi-conjugation, and the degree of the shift was proportional to the number of acetylene group in the side chain. The value of chi^<(3)> was ca.10^<-9> esu, which was increased about one order of magnitude greater than ordinary polydiacetykenes.