Synthesis and electrochromic properties of polyamines containing a 4,4′-diaminotriphenylamine-<i>N</i>,<i>N</i>′-diyl unit in the polymer backbone: Ru-catalyzed N?H insertion polycondensation of 1,4-phenylenebis(diazoacetate) with 4,4′-diaminotriphenylami
Synthesis and electrochromic properties of polyamines containing a 4,4′-diaminotriphenylamine-<i>N</i>,<i>N</i>′-diyl unit in the polymer backbone: Ru-catalyzed N?H insertion polycondensation of 1,4-phenylenebis(diazoacetate) with 4,4′-diaminotriphenylami
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聚合物骨架中含有4,4-二氨基三苯胺-<i>N</i>,<i>N</i>-二基单元的多胺的合成及电致变色性能：Ru催化的N?H插入缩聚1,4-亚苯基双（重氮乙酸酯）与 4,4-二氨基三苯胺
DOI：
10.1039/d2py01118b
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发表时间：
2022
影响因子：
4.6
通讯作者：
Ihara Eiji
中科院分区：
文献类型：
--
作者：
Wang Yun-Chi;Shao Yu-Jen;Liou Guey-Sheng;Nagao Sota;Makino Yusuke;Akiyama Eita;Kato Masaaki;Shimomoto Hiroaki;Ihara Eiji
以钌为催化剂，通过双（重氮羰基）化合物与4，4 ′-二氨基三苯胺的缩聚反应，合成了一种主链含4，4 ′-二氨基三苯胺-N，N′-二基单元的新型多胺.在本研究中新制备的定义明确的多胺中，二胺单体中的两个伯氨基保留为聚合物主链中的仲氨基，与先前报道的通过相同二胺单体的缩聚制备的聚合物相反，其中氨基被并入酰胺或酰亚胺键中。在聚合物主链中得到的三苯基氨基框架具有三个氨基，每个氨基可以独立地参与电化学过程，作为氧化还原中心与施加的电化学电势。用循环伏安法和光谱电化学方法研究了多胺薄膜和电致变色器件的电致变色性能，发现多胺确实经历了预期的三阶段氧化还原过程。
A new type of polyamine containing a 4,4′-diaminotriphenylamine-N,N′-diyl unit in the main chain was prepared by Ru-catalyzed polycondensation of a bis(diazocarbonyl) compound with 4,4′-diaminotriphenylamine, where the propagation is N–H insertion of a carbene–carbon atom generated from the diazocarbonyl group of the former monomer with N2 elimination. In the well-defined polyamines newly prepared in this study, the two primary amino groups in the diamine monomer remain as secondary amino groups in the polymer main chain, in contrast to the previously reported polymers prepared by polycondensation of the same diamine monomers, where the amino groups were incorporated into an amide or imide linkage. The resulting triphenyl amino framework in the polymer main chain possesses three amino groups, each of which can independently participate in the electrochemical process as a redox center with applied electrochemical potentials. The electrochromic properties of thin films and electrochromic devices of the polyamines were evaluated with cyclic voltammetry and spectroelectrochemistry, revealing that the polyamines indeed underwent an expected three-stage redox process.