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Design and synthesis of a novel azobenzene-containing polymer both in the main- and side-chain toward unique photocontrolled isomerization properties†
Materials Chemistry Frontiers ( IF 7 ) Pub Date : 2018-03-21 00:00:00 , DOI: 10.1039/c8qm00035b
Kai Wang 1, 2, 3, 4, 5 , Lu Yin 1, 2, 3, 4, 5 , Tengfei Miu 1, 2, 3, 4, 5 , Meng Liu 1, 2, 3, 4, 5 , Yin Zhao 1, 2, 3, 4, 5 , Yang Chen 1, 2, 3, 4, 5 , Nianchen Zhou 1, 2, 3, 4, 5 , Wei Zhang 1, 2, 3, 4, 5 , Xiulin Zhu 1, 2, 3, 4, 5
Affiliation  

Azobenzene (Azo)-containing polymers have been widely exploited due to their unique reversible transcis photoisomerization properties driven by UV/Vis or all visible light. Herein, the copolymer AzoF8-alt-Azo was designed and synthesized, which contained Azo units both in the main- and side-chain. The π–π* band maximum absorption of the side-chain Azo (s-Azo) trans-isomer locates at 360 nm (UV region), and the n–π* band maximum absorption is near 450 nm (Vis region). The π–π* band maximum absorption of the main-chain Azo (m-Azo) trans-isomer locates at 425 nm (Vis region), and the n–π* band maximum absorption is near 520 nm (Vis region). The separation of absorptions of the π–π* bands of the trans-isomers and the n–π* bands of the cis-isomer of the s- and m-Azo units endows the possibility to control the photoisomerization behaviour of different Azo units in the main- and side-chain. The structural changes were achieved upon alternating photoirradiation in the order of 365 nm light (cis-form of s-Azo and trans-form of m-Azo, SC-MT), 435 nm light (trans-form of s-Azo and cis-form of m-Azo, ST-MC), and 546 nm light (trans-form of s- and m-Azo, ST-MT), which were monitored by UV-Vis spectroscopy. This indicates that three forms, SC-MT, ST-MC and ST-MT in same polymer chain can be successfully obtained by the above strategy. Furthermore, upon the irradiation in the order of 313 nm, 405 nm, 435 nm and 536 nm light, four forms, ST-MT, SC-MT, SC-MC and ST-MC, were successfully achieved in the same AzoF8-alt-Azo chain. These interesting findings will not only expand the photoisomerization behaviours of Azo-containing polymers, but also give cues for the design of novel optical materials.

中文翻译:

设计和合成新颖的主链和侧链含偶氮苯的聚合物,以实现独特的光控异构化性能

含偶氮(Azo)的聚合物因其独特的可逆反-顺式光异构化特性而受到广泛开发,该特性是由UV / Vis或所有可见光驱动的。本文中,设计并合成了共聚物AzoF8- alt- Azo ,该共聚物在主链和侧链中均包含Azo单元。侧链偶氮(s-Azo)反式异构体的π–π *带最大吸收位于360 nm(紫外区域),而n–π *带最大吸收接近450 nm(可见区)。主链偶氮(m-Azo)反式异构体的π–π *带最大吸收位于425 nm(Vis区域),而n–π *带最大吸收位于520 nm(Vis区域)附近。分子的π–π *吸收带的分离s-和m-Azo单元的顺式异构体的反式异构体和n-π*带赋予了控制主链和侧链中不同Azo单元的光致异构化行为的可能性。结构变化是通过在365 nm的光(s-Azo的顺式和m-Azo的反式,SC-MT),435 nm的光(s-Azo和顺式的反式)交替进行光辐照后实现的的构型中间-偶氮,ST-MC)和546纳米的光(-和-偶氮形式,ST-MT),通过紫外-可见光谱法进行监测。这表明通过上述策略可以成功地获得同一聚合物链中的三种形式,即SC-MT,ST-MC和ST-MT。此外,在以313 nm,405 nm,435 nm和536 nm的顺序进行辐照时,在相同的AzoF8- alt中成功实现了ST-MT,SC-MT,SC-MC和ST-MC四种形式-偶氮链。这些有趣的发现不仅将扩大含偶氮聚合物的光致异构化行为,而且还将为新型光学材料的设计提供线索。
更新日期:2018-03-21
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