Five-Stage Near-Infrared Electrochromism in Electropolymerized Films Composed of Alternating Cyclometalated Bisruthenium and Bis-triarylamine Segments
Five-Stage Near-Infrared Electrochromism in Electropolymerized Films Composed of Alternating Cyclometalated Bisruthenium and Bis-triarylamine Segments
复制标题
环金属化双钌和双三芳胺交替链段电聚合薄膜的五阶段近红外电致变色
DOI：
10.1021/ic401288g
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发表时间：
2013-09-02
影响因子：
4.6
通讯作者：
Yao, Jiannian
中科院分区：
文献类型：
--
作者：
Yao, Chang-Jiang;Zhong, Yu-Wu;Yao, Jiannian
环化双钌配合物[（Nptpy）（2）Ru-2（tpyr）]（PF_6）（2）和[（Nptpy）（2）Ru-2（tpb）]（PF_6）（2）的氧化电聚合在电极表面产生了粘附的金属离子聚合物膜，其中Nptpy为4 ′. (p-N N-二苯基氨基）苯基1 - 2，2 ′：6 ′，2 ″-三联吡啶，tpyr是1，3，6，8-四（吡啶-2-基）芘的2，7-双去质子化形式，tpb是1，2，4，5-四（吡啶-2-基）苯的3，6-双去质子化形式。所得聚合物由两种类型的交替组成单元组成：tpyr-或Apb-桥接的环化双钌单元和联苯桥接的双-三芳基胺片段。由于这两个单元的分步氧化，这些膜呈现出四对界限分明的阳极氧化还原电对。通过控制混合价双三芳胺和双三芳胺单元的价间电荷转移跃迁，实现了五阶近红外电致变色，并具有良好的对比度和显色效率。通过扫描电子显微镜和X射线光电子能谱技术的薄膜表征。
Oxidative electropolymerization of cyclometalated bisruthenium complexes [(Nptpy)(2)Ru-2(tppyr)](PF6)(2) and [(Nptpy)(2)Ru-2(tpb)](PF6)(2) produced adherent metal, lopolymeric films on electrode surfaces, where Nptpy is 4'.. (p-N,N-diphenylamino)pheny1-2,2':6',2"-terpyridine, tppyr is the 2,7-bisdeprotonated form of 1,3,6,8-tetra(pyrid-2-yI)pyrene, and tpb is the 3,6-bisdeprotonated form of 1,2,4,5tetra(pyrid-2-yl)benzene. The resulting polymers are composed of two types of alternating constituent units: tppyr- or Apb-bridged cyclometalated bisruthenium units and biphenylbridged bis-triarylamine segments. These films exhibited four .well-defined anodic redox couples as a result of the stepwise oxidations of these two units. By manipulating the intervalence charge-transfer transitions of mixed-valent bisrutheniurn and bis-triarylamine units, five-stage near-infrared electrochromism with stepwise color, changes accompanied by good contrast ratio and coloration efficiency has been realized in these films. The film characterization by scanning electronic microscopy and X-ray photoelectron spectroscopy techniques are presented as well.