Synthesis of π-conjugated polymer containing both thiophene and phosphole sulfide in the main chain by simultaneous post-element transformation of organotitanium polymer
Synthesis of π-conjugated polymer containing both thiophene and phosphole sulfide in the main chain by simultaneous post-element transformation of organotitanium polymer
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DOI：
10.1002/pola.29522
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发表时间：
2019-10-16
影响因子：
--
通讯作者：
Tomita, Ikuyoshi
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文献类型：
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作者：
Matsumura, Yoshimasa;Nishiyama, Hiroki;Tomita, Ikuyoshi
本文报道了一种含钛环戊二烯-2，5-二基单元的区域规整有机金属聚合物经元素后转换，合成了主链上同时含有噻吩和1-苯基磷杂环戊二烯硫醚单元（多个杂环）的π共轭聚合物，并研究了其独特的光电性能。通过有机钛聚合物与一氯化硫和二氯苯膦（各0.6当量）的同时反应，以73%的产率获得了含有多个杂环的π共轭聚合物，其数均分子量（M-n）和分子量分布（M-w/M-n）通过尺寸排阻色谱（SEC）分别估计为11，000和3.4。由此获得的π-共轭聚合物被发现具有高的HOMO和低的LUMO能级，由于富电子的噻吩和缺电子的磷杂茂硫化物单元，分别由其循环伏安法（CV）分析支持。与含噻吩单元的聚合物和含硫代磷杂环戊二烯单元的聚合物的混合物相比，含多个杂环的π共轭聚合物表现出有趣的光学性质。例如，在光致发光光谱中在608 nm处观察到特定的发射峰，这在含噻吩聚合物、含磷杂环戊烯聚合物和它们的混合物的情况下没有观察到。(c)2019 Wiley Periodicals，Inc. J.波利姆科学，A部分：聚合物2019年化学
The synthesis and unique optoelectronic features of a pi-conjugated polymer containing both thiophene and 1-phenylphosphole sulfide units (multiple heteroles) in the main chain by the post-element transformation of a regioregular organometallic polymer possessing titanacyclopentadiene-2,5-diyl unit are described. The pi-conjugated polymer containing multiple heteroles was obtained in 73% yield by the simultaneous reaction of the organotitanium polymer with sulfur monochloride and dichlorophenylphosphine (0.6 equiv each), whose number-average molecular weight (M-n) and the molecular-weight distribution (M-w/M-n) were estimated to be 11,000 and 3.4, respectively, by the size exclusion chromatography (SEC). The pi-conjugated polymer thus obtained was found to have the high HOMO and the low LUMO energy levels due to the electron-rich thiophene and electron-deficient phosphole sulfide units, respectively, as supported by its cyclic voltammetry (CV) analysis. Compared to a mixture of a polymer containing sole thiophene-unit and that containing sole phosphole sulfide units, the pi-conjugated polymer-containing multiple heteroles proved to exhibit interesting optical properties. For example, a specific emission peak was observed at 608 nm in the photoluminescence spectrum, which was not observed in the case of the thiophene-containing polymer, the phosphole-containing polymer, and their mixture. (c) 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019