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Azobenzene-containing Alternating and Random Metathesis Copolymers toward Gaining More Insight into Photoisomerization Properties
Macromolecules ( IF 5.1 ) Pub Date : 2021-09-21 , DOI: 10.1021/acs.macromol.0c02621
Wei Song 1 , Xiaotian Qu 1 , Yadi Li 1 , Juan Li 1 , Chengshuang Wang 1 , Liang Ding 1
Affiliation  

Using alternating diene metathesis (ALTMET) polycondensation and acyclic diene metathesis (ADMET) polymerization, two kinds of alternating and random copolymers from electron-deficient azobenzene (azo)-functionalized α,ω-diene monomers that are photoresponsive molecules and comonomers such as electron-rich carbazole or fluorene-functionalized diene or diacrylate monomers were synthesized. All of these copolymers were tailored to explore the effects of alternating and random monomer sequences and electron transfer capability on the self-assembly morphology and photoresponsive properties. As expected, the distinct absorption features from azo units in these copolymers are observed in their optical spectra, which cannot be achieved by traditional azo-containing homo- and copolymers. Because of the presence of stiff and electron-rich carbazole or fluorene motifs, the ability and efficiency of photoisomerization was depressed to some extent according to the sequential differences of two monomers and the electron effect in the copolymer chain. Moreover, the sizes and morphologies of alternating copolymers can be modulated through the methylene spacer and sequence of rigid conjugated motifs generating diverse nanostructures leading to a different chain mobility, which ultimately exhibited the unique photoisomerization behaviors. These interesting findings not only demonstrate a facile and efficient method for constructing azo-carbazole and azo-fluorene metathesis copolymers but also expand the optical properties of azo-containing polymers.

中文翻译:

含偶氮苯交替和无规复分解共聚物以更深入地了解光异构化特性

采用交替二烯复分解 (ALTMET) 缩聚和无环二烯复分解 (ADMET) 聚合,由缺电子偶氮苯 (azo)-官能化的 α,ω-二烯单体和电子-等共聚单体形成两种交替和无规共聚物。合成了富含咔唑或芴官能化的二烯或二丙烯酸酯单体。所有这些共聚物都经过定制,以探索交替和随机的单体序列和电子转移能力对自组装形态和光响应性能的影响。正如预期的那样,这些共聚物中偶氮单元的独特吸收特征在它们的光谱中观察到,这是传统的含偶氮均聚物和共聚物无法实现的。由于刚性和富电子咔唑或芴基序的存在,根据两种单体的顺序差异和共聚物链中的电子效应,光异构化的能力和效率在一定程度上受到抑制。此外,交替共聚物的尺寸和形态可以通过亚甲基间隔基和刚性共轭基序序列进行调节,产生不同的纳米结构,导致不同的链迁移率,最终表现出独特的光异构化行为。这些有趣的发现不仅证明了一种构建偶氮咔唑和偶氮芴复分解共聚物的简便有效的方法,而且还扩展了含偶氮聚合物的光学性能。由于两种单体的顺序差异和共聚物链中的电子效应,光异构化的能力和效率在一定程度上受到抑制。此外,交替共聚物的尺寸和形态可以通过亚甲基间隔基和刚性共轭基序序列进行调节,产生不同的纳米结构,导致不同的链迁移率,最终表现出独特的光异构化行为。这些有趣的发现不仅证明了一种构建偶氮咔唑和偶氮芴复分解共聚物的简便有效的方法,而且还扩展了含偶氮聚合物的光学性能。由于两种单体的顺序差异和共聚物链中的电子效应,光异构化的能力和效率在一定程度上受到抑制。此外,交替共聚物的尺寸和形态可以通过亚甲基间隔基和刚性共轭基序序列进行调节,产生不同的纳米结构,导致不同的链迁移率,最终表现出独特的光异构化行为。这些有趣的发现不仅证明了一种构建偶氮咔唑和偶氮芴复分解共聚物的简便有效的方法,而且还扩展了含偶氮聚合物的光学性能。交替共聚物的尺寸和形态可以通过亚甲基间隔基和刚性共轭基序序列进行调节,产生不同的纳米结构,导致不同的链迁移率,最终表现出独特的光异构化行为。这些有趣的发现不仅证明了一种构建偶氮咔唑和偶氮芴复分解共聚物的简便有效的方法,而且还扩展了含偶氮聚合物的光学性能。交替共聚物的尺寸和形态可以通过亚甲基间隔基和刚性共轭基序序列进行调节,产生不同的纳米结构,导致不同的链迁移率,最终表现出独特的光异构化行为。这些有趣的发现不仅证明了一种构建偶氮咔唑和偶氮芴复分解共聚物的简便有效的方法,而且还扩展了含偶氮聚合物的光学性能。
更新日期:2021-10-12
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