Metathesis Cyclopolymerization Triggered Self-Assembly of Azobenzene-Containing Nanostructure.
Metathesis Cyclopolymerization Triggered Self-Assembly of Azobenzene-Containing Nanostructure.
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复分解环聚合引发含偶氮苯纳米结构的自组装
DOI：
10.3390/molecules25173767
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发表时间：
2020-08-19
期刊：
影响因子：
--
通讯作者：
Wu J
中科院分区：
文献类型：
--
作者：
Song W;Shen J;Li X;Huang J;Ding L;Wu J
将偶氮苯（AB）单元成功地引入到聚1，6-庚二炔中，以保证双链和单链聚1，6-庚二炔（P1和P2）的顺利合成，同时实现AB功能化的双（1，6-庚二炔）和1，6-庚二炔单体（M1和M2）通过Grubbs-III催化剂介导的复分解环聚合（CP）的自组装。单体和聚合物，其特征在于通过1H NMR，质谱，和GPC技术。双链聚（1，6-庚二炔）具有大尺度的有序梯形纳米结构。这一结果归因于端基之间沿聚合物纵轴沿着的π−π吸引力和相邻聚合物主链之间的货车范德华相互作用。而偶氮生色团连接在P2的侧链上，在CP过程中诱导胶束纳米结构的构象，无需任何后处理。此外，偶氮单元的光异构化对聚合物主链的共轭度有明显不同的调节作用，尤其是对单链P2的调节作用，这是由于聚合物中AB生色团的结构差异和相互作用所致.
Azobenzene (AB) units were successfully introduced into poly(1,6-heptadiyne)s in order to ensure smooth synthesis of double- and single-stranded poly(1,6-heptadiyne)s (P1 and P2) and simultaneously realize the self-assembly by Grubbs-III catalyst-mediated metathesis cyclopolymerization (CP) of AB-functionalized bis(1,6-heptadiyne) and 1,6-heptadiyne monomers (M1 and M2). Monomers and polymers were characterized by 1H NMR, mass spectroscopy, and GPC techniques. The double-stranded poly(1,6-heptadiyne)s exhibited a large scale of ordered ladder nanostructure. This result was attributed to the π−π attractions between end groups along the longitudinal axis of the polymers and van der Waals interactions between the neighboring polymeric backbones. While the Azo chromophore connected in the side chain of P2 induced conformation of micelles nanostructure during the CP process without any post-treatment. Furthermore, the photoisomerization of Azo units had an obviously different regulatory effect on the conjugated degree of the polymer backbone, especially for the single-stranded P2, which was attributed to the structural differences and the interaction between AB chromophores in the polymers.
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