Self-Doped Polyphenylenes Containing Electron-Accepting Viologen Side Group
Self-Doped Polyphenylenes Containing Electron-Accepting Viologen Side Group
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DOI：
10.1021/ma900522w
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发表时间：
2009-04
期刊：
影响因子：
5.5
通讯作者：
I. Yamaguchi;N. Mizoguchi;Moriyuki Sato
中科院分区：
文献类型：
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作者：
I. Yamaguchi;N. Mizoguchi;Moriyuki Sato
以2，5-二溴苯胺、9，9-二己基芴-2，7-二硼酸双（1，3-丙二醇）酯和2，6-二辛氧基苯-1，4-二硼酸为原料，在钯配合物催化下合成了含NH 2侧基的聚苯撑（PPs），即PFluNH 2和PPhNH 2。PFluNH 2和PPhNH 2与1-烷基-1 ′-（2，4-二硝基苯基）-4，4 ′-联吡啶二氯化物（烷基=乙基和正己基）反应，消除2，4-二硝基苯胺，生成带有紫精（1，1 ′-二取代4，4 ′-联吡啶二阳离子）侧基的PP，即PFluBPyHex、PFluBPyEt和PPhBPyEt。PFluBPyHex、PFluBPyEt和PPhBPyEt的紫外-维斯光谱显示，由于紫精自由基阳离子在氮气下通过电子从聚合物主链转移到紫精部分而形成，导致了吸收。与光致发光的PFluNH 2和PPhNH 2相反，PFluBPyHex、PFluBPyEt和PPhBPyEt没有显示光致发光，因为它们中所含的紫精起猝灭剂的作用。PFluBPyEt和PPhBPyEt的ESR谱证实了它们的生成。
Polyphenylenes (PPs) with NH2 side groups, namely, PFluNH2 and PPhNH2, were synthesized by the Pd-complex-catalyzed reaction of 2,5-dibromoaniline with 9,9-dihexylfluorene-2,7-diboronic acid bis(1,3-propanediol) ester and 2,6-dioctyloxybenzene-1,4-diboronic acid. The reaction of PFluNH2 and PPhNH2 with 1-alkyl-1′-(2,4-dinitrophenyl)-4,4′-bipyridinium dichloride (alkyl = ethyl and n-hexyl) eliminated 2,4-dinitroaniline to yield PPs with viologen (1,1′-disubstituted 4,4′-bipyridinium dications) side groups, namely, PFluBPyHex, PFluBPyEt, and PPhBPyEt. The UV−vis spectra of PFluBPyHex, PFluBPyEt, and PPhBPyEt showed absorptions due to the viologen radical cation that was formed under nitrogen by the electron transfer from the polymer backbone to the viologen moiety. In contrast to photoluminescent PFluNH2 and PPhNH2, PFluBPyHex, PFluBPyEt, and PPhBPyEt showed no photoluminescence because the viologen contained within them acted as a quencher. The ESR spectra of PFluBPyEt and PPhBPyEt confirmed the generation...