Unusual Doping of Donor-Acceptor-Type Conjugated Polymers Using Lewis Acids
Unusual Doping of Donor-Acceptor-Type Conjugated Polymers Using Lewis Acids
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DOI：
10.1021/ja501024n
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发表时间：
2014-04-02
影响因子：
15
通讯作者：
Bendikov, Michael
中科院分区：
文献类型：
--
作者：
Poverenov, Elena;Zamoshchik, Natalia;Bendikov, Michael
设计了可以进行不寻常的非氧化掺杂的共轭聚合物。一系列基于供体-受体-供体（DAD）部分2,1,3-苯并硒二唑、2,1,3-苯并噻二唑、2,1,3-苯并恶二唑苯并[2,1,5]氧二唑和2-己基苯并三唑作为受体片段和3,4-乙烯二氧基硒吩的聚合物 (EDOS)和3,4-乙撑二氧噻吩(EDOT)作为供体片段被制备。当所研究的聚合物与路易斯酸和碱反应时，观察到显着的光学开关和电导率变化，证明了有效非氧化掺杂/去掺杂的特殊情况。值得注意的是，在之前报道的工作中，路易斯酸的配位会导致带隙移动，但不会引起导电聚合物的掺杂，而在本研究中，路易斯酸与高供体 EDOT 和 EDOS 部分的配位会导致聚合物掺杂。这些聚合物在从中性状态到掺杂状态的多次转换循环后表现出显着的稳定性，反之亦然，并且可以通过电化学和化学方式进行转换。研究了所制备的聚合物与不同强度的路易斯酸和碱的反应性。路易斯酸配位模式及其对聚合物能量和带隙的影响的计算研究支持了不寻常的掺杂。报道的掺杂方法开辟了在不氧化的情况下控制共轭聚合物的共轭、颜色变化和状态转换的可能性。
Conjugated polymers that can undergo unusual nonoxidative doping were designed. A series of polymers based on donor-acceptor-donor (DAD) moieties 2,1,3-benzoselenadiazole, 2,1,3-benzothiadiazole, 2,1,3-benzoxadiazolebenzo[2,1,5]oxodiazole, and 2-hexylbenzotriazole as acceptor fragments and 3,4-ethylenedioxyselenophene (EDOS) and 3,4-ethylenedioxythiophene (EDOT) as donor fragments was prepared. When the studied polymers were reacted with Lewis acids and bases, notable optical switching and conductivity changes were observed, evidencing the exceptional case of efficient nonoxidative doping/dedoping. Remarkably, in previously reported works, coordination of Lewis acids causes band gap shift but not doping of the conductive polymer, while in the present study, coordination of Lewis acid to highly donating EDOT and EDOS moieties led to polymer doping. The polymers show remarkable stability after numerous switching cycles from neutral to doped states and vice versa and can be switched both electrochemically and chemically. The reactivity of the prepared polymers with Lewis acids and bases of different strengths was studied. Calculation studies of the Lewis acid coordination mode, its effect on polymer energies and band gap, support the unusual doping. The reported doping approach opens up the possibility to control the conjugation, color change, and switching of states of conjugated polymers without oxidation.