Metathesis Cyclopolymerization of 1,6-Heptadiyne Derivative toward Triphenylamine-Functionalized Polyacetylene with Excellent Optoelectronic Properties and Nanocylinder Morphology
Metathesis Cyclopolymerization of 1,6-Heptadiyne Derivative toward Triphenylamine-Functionalized Polyacetylene with Excellent Optoelectronic Properties and Nanocylinder Morphology
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1,6-庚二炔衍生物复分解环聚合制备具有优异光电性能和纳米柱形貌的三苯胺官能化聚乙炔
DOI：
10.1021/acs.macromol.5b00379
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发表时间：
2015-04-28
期刊：
影响因子：
5.5
通讯作者：
Liao, Xiaojuan
中科院分区：
文献类型：
--
作者：
Guo, Mengfang;Sun, Ruyi;Liao, Xiaojuan
1,6-庚二炔衍生物的复分解环聚合很容易通过第三代Grubbs催化剂合成三苯胺官能化聚乙炔（TPA-PA），选择性地生成具有五元环和全反式微观结构的TPA-PA。 TPA悬垂体赋予PA良好的溶解度和优异的光电性能（在CHCl3中最大吸收波长为592-605 nm，HOMO能级约为-5.04 eV，能带隙为1.82-1.77 eV）。当双-TPA侧基引入PA主链时，所得聚合物poly(M2)在PA衍生物家族中表现出理想的氧化稳定性（在THF中储存长达30天）和高荧光量子产率（高达12.3%）。此外，poly(M2) 可以自发地自组装成纳米圆柱结构，而不需要任何繁琐的合成后处理。这是首次报道刚性且不可移动的共轭PA链段借助TPA侧基的pp相互作用组装成新型圆柱形纳米结构。
Metathesis cyclopolymerization of 1,6-heptadiyne derivatives is readily utilized to synthesize triphenylamine-functionalized polyacetylenes (TPA-PAs) by a third-generation Grubbs catalyst, which selectively generated TPA-PAs with a five-membered ring and all-trans microstructure. The TPA pendants endowed PAs with good solubility and excellent optoelectronic properties (maximum absorption wavelength of 592-605 nm in CHCl3, HOMO level of around -5.04 eV, and energy bandgap of 1.82-1.77 eV). When bis-TPA side group was introduced into the PA backbone, the resultant polymer, poly(M2), displayed desirable oxidative stability (up to 30 days stored in THF) and high fluorescence quantum yield (up to 12.3%) in the family of PA derivatives. In addition, poly(M2) could spontaneously self-assemble into the nanocylinder architecture without requiring any tedious postsynthetic treatments. This is the first report that the rigid and immobile conjugated PA segment assembled into the novel cylindrical nanostructure with the aid of pp interaction of TPA side group.