Synthesis and Chemical Properties of Polyphenylenes Cross-linked by Electron-accepting Viologen Moiety,
Synthesis and Chemical Properties of Polyphenylenes Cross-linked by Electron-accepting Viologen Moiety,
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电子接受紫精基团交联聚亚苯基的合成及化学性能，
DOI：
10.1007/s00289-015-1579-x
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
M. Yamamoto
中科院分区：
文献类型：
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作者：
I. Yamaguchi;M. Yamamoto
以钯配合物为催化剂，以2，5-二溴苯胺和9，9-二己基芴-2，7-二硼酸双（1，3-丙二醇）酯为原料，合成了含NH 2侧基的聚苯（PP），即聚合物-1。聚合物-1与1，1 ′-双（2，4-二硝基苯基）-4，4 ′-联吡啶二氯化物（盐-1）以1：0.5、1：1和1：2的摩尔比反应消除了2，4-二硝基苯胺，分别得到由紫精（1，1 ′-二取代4，4 ′-联吡啶二价阳离子）部分交联的PP、聚合物-2a、聚合物-2b和聚合物-2c。聚合物-2c的紫外-可见光谱显示出由于电子从聚合物主链转移到紫精部分而形成的紫精自由基阳离子引起的吸收。聚合物-2c的p型掺杂状态在空气中是稳定的。聚合物-2c的ESR谱证实了紫精自由基的产生。与photoluminescentpolymer-1相反，由紫精部分交联的聚合物没有显示出光致发光，因为其中所含的紫精起猝灭剂的作用。由于聚合物2c的自掺杂作用，聚合物2c的导电性高于聚合物1。
Polyphenylene (PP) with NH2side groups, namely,polymer-1, was synthesized by the Pd-complex-catalyzed reaction of 2,5-dibromoaniline with 9,9-dihexylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester. The reaction ofpolymer-1with 1,1′-bis(2,4-dinitrophenyl)-4,4′-bipyridinium dichloride (salt-1) in 1:0.5, 1:1, and 1:2 molar ratios eliminated 2,4-dinitroaniline to yield PPs cross-linked by a viologen (1,1′-disubstituted 4,4′-bipyridinium dications) moiety,polymer-2a,polymer-2b, andpolymer-2c, respectively. The UV–vis spectrum ofpolymer-2cshowed absorptions due to the viologen radical cation formed by electron transfer from the polymer backbone to the viologen moiety. The p-doping state ofpolymer-2cwas stable in air. The ESR spectrum ofpolymer-2cconfirmed the generation of the viologen radical. In contrast to photoluminescentpolymer-1, the polymers cross-linked by a viologen moiety showed no photoluminescence because the viologen contained within them acted as a quencher. The electrical conductivity of the pellet molded frompolymer-2cwas higher than that ofpolymer-1due to the self-doping inpolymer-2c.