Organometallic Synthesis of n-Type π-Conjugated Polymers with Pendant Cation Trapping Sites and Their Stability of n-Doping State Against Air
Organometallic Synthesis of n-Type π-Conjugated Polymers with Pendant Cation Trapping Sites and Their Stability of n-Doping State Against Air
复制标题
具有侧挂阳离子捕获位点的n型π共轭聚合物的有机金属合成及其n掺杂态对空气的稳定性
DOI：
10.1002/pi.4361
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发表时间：
2013
影响因子：
3.2
通讯作者：
Ryouhei Uehara
中科院分区：
文献类型：
--
作者：
Isao Yamaguchi;Ryouhei Uehara
采用金属有机缩聚法合成了由1，2，4-三唑环的4-位取代苯并-15-冠-5-醚(苯并15C5)亚单位的1，2，4-三氮唑环和2，1，3-苯并噻二唑-4，7-二基环等n型π共轭聚合物。聚合物的紫外可见光谱在比3，5‐bis(2‐bromopyridyl)‐4‐benzo15C5‐1，2，4‐triazole，更长的波长处出现吸收极大值(λ最大值)，这表明它们的π共轭体系是沿着聚合物链扩展的。含苯并15C5亚基的聚合物经历了电化学还原(n掺杂)，相应的氧化(n脱掺杂)在乙腈NaClO4溶液中以异常高的电位发生；导致异常高氧化电位的因素是稳定的n掺杂状态，这归因于15C5环中包含Na+。含苯并15C5亚基的聚合物在空气中表现出比不含该亚基的聚合物更高的n掺杂稳定性。版权所有©2012中国化学工业学会
n‐Type π‐conjugated polymers comprising a 1,2,4‐triazole ring substituted by a benzo‐15‐crown 5‐ether (benzo15C5) subunit at the 4‐position of the 1,2,4‐triazole ring and n‐type aromatic rings such as pyridine‐2,5‐diyl and 2,1,3‐benzothiadiazole‐4,7‐diyl rings were synthesized by organometallic polycondensation. The UV‐visible spectra of the polymers exhibited absorption maxima (λmaxvalues) at a longer wavelength than that exhibited by 3,5‐bis(2‐bromopyridyl)‐4‐benzo15C5‐1,2,4‐triazole, revealing that their π‐conjugation system was expanded along the polymer chain. The polymers with the benzo15C5 subunit underwent an electrochemical reduction (n‐doping), and the corresponding oxidation (n‐dedoping) occurred at an unusually high potential in an acetonitrile solution of NaClO4; the factor responsible for the unusually high oxidation potential was the stabilized n‐doping state that was attributed to the inclusion of Na+in the 15C5 ring. The polymers with the benzo15C5 subunit exhibited a considerably higher stability of the n‐doping state in air than did those without this subunit. Copyright © 2012 Society of Chemical Industry