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通过后元素转化技术制备含砷卟啉的π共轭聚合物。

Arsole-Containing π-Conjugated Polymer by the Post-Element-Transformation Technique.

机构信息

School of Materials and Chemical Technology, Tokyo Institute of Technology, Nagatsuta-cho 4259-G1-9, Midori-ku, Yokohama, 226-8502, Japan.

Graduate School of Science and Technology, Kyoto Institute of Technology, Goshokaido-cho, Matsugasaki, Sakyo-ku, Kyoto, 606-8585, Japan.

出版信息

Angew Chem Int Ed Engl. 2016 Nov 21;55(48):15040-15043. doi: 10.1002/anie.201608404. Epub 2016 Nov 7.

Abstract

A synthetic method to obtain an arsole-containing π-conjugated polymer by the post-transformation of the organotitanium polymer titanacyclopentadiene-2,5-diyl unit with an arsenic-containing building block is described. The UV/Vis absorption maximum and onset of the polymer were observed at 517 nm and 612 nm, respectively. The polymer exhibits orange photoluminescence with an emission maximum (E ) of 600 nm and the quantum yield (Φ) of 0.05. The polymer proved to exhibit a quasi-reversible redox behavior in its cyclic voltammetric (CV) analysis. The energy levels of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were estimated to be -5.43 and -3.24 eV, respectively, from the onsets for oxidation and reduction signals in the CV analysis. Further chemical modification of the arsole unit in the π-conjugated polymer by complexation of gold(I) chloride occurred smoothly resulting in the bathochromic shift of the UV/Vis absorption and lowering of the LUMO energy level.

摘要

一种通过含砷砌块对有机钛聚合物钛杂环戊二烯-2,5-二基单元进行后转化来获得含胂的π共轭聚合物的合成方法。聚合物的 UV/Vis 吸收最大值和起始波长分别观察到在 517nm 和 612nm。聚合物表现出橙色光致发光,发射最大值 (E) 为 600nm,量子产率 (Φ) 为 0.05。聚合物在循环伏安 (CV) 分析中表现出准可逆的氧化还原行为。通过 CV 分析中氧化和还原信号的起始,估算出最高占据分子轨道 (HOMO) 和最低未占据分子轨道 (LUMO) 的能级分别为-5.43 和-3.24eV。进一步通过金(I)氯化物对π共轭聚合物中胂单元的化学修饰,反应顺利进行,导致 UV/Vis 吸收的红移和 LUMO 能级的降低。

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