{"title":"Photoinduced Anisotropy in Thin Films of Azobenzene-Containing Liquid Crystalline Supramolecular Complexes of Various Polymer Architecture.","authors":"Miron Bugakov, Valery Shibaev, Natalia Boiko","doi":"10.1002/cphc.202400677","DOIUrl":null,"url":null,"abstract":"<p><p>Light patternable colorless liquid crystalline (LC) polymers are promising materials for functional photonic devices with broad applications in optical communication, diffractive optics, and displays. This work reports photoinduced optical anisotropy in thin films of azobenzene-containing (Azo) LC block copolymer supramolecular complexes, which can be decolorized after light patterning providing colorless patterned birefringent polymer films. The supramolecular complexes are prepared via intermolecular pyridine-phenol hydrogen bonding between a low-molecular-weight Azo phenol and host LC AB diblock and ABA triblock copolymers consisted of LC phenylbenzoate (PhM) blocks and poly(vinylpyridine) units. The molecular architecture of the host polymers and the morphological pattern formed by the complexes can affect orientational behavior of Azo groups under irradiation with linearly polarized light. Photoorientation of hydrogen-bonded Azo groups is accompanied by the cooperative orientation of non-photochromic PhM units, which form individual microphases and stabilize the orientation of Azo groups. This effect is specific for block copolymer complexes and it is absent for random copolymer complex, which is used as a reference sample. Optical anisotropy induced in films of the block copolymer complexes can be amplified by heating above the glass transition temperature and subsequent rinsing with diethyl ether allows colorless birefringent polymer films to be prepared.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400677"},"PeriodicalIF":2.3000,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemphyschem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cphc.202400677","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/11/5 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Light patternable colorless liquid crystalline (LC) polymers are promising materials for functional photonic devices with broad applications in optical communication, diffractive optics, and displays. This work reports photoinduced optical anisotropy in thin films of azobenzene-containing (Azo) LC block copolymer supramolecular complexes, which can be decolorized after light patterning providing colorless patterned birefringent polymer films. The supramolecular complexes are prepared via intermolecular pyridine-phenol hydrogen bonding between a low-molecular-weight Azo phenol and host LC AB diblock and ABA triblock copolymers consisted of LC phenylbenzoate (PhM) blocks and poly(vinylpyridine) units. The molecular architecture of the host polymers and the morphological pattern formed by the complexes can affect orientational behavior of Azo groups under irradiation with linearly polarized light. Photoorientation of hydrogen-bonded Azo groups is accompanied by the cooperative orientation of non-photochromic PhM units, which form individual microphases and stabilize the orientation of Azo groups. This effect is specific for block copolymer complexes and it is absent for random copolymer complex, which is used as a reference sample. Optical anisotropy induced in films of the block copolymer complexes can be amplified by heating above the glass transition temperature and subsequent rinsing with diethyl ether allows colorless birefringent polymer films to be prepared.
可光照图案化的无色液晶(LC)聚合物是功能性光子器件的理想材料,在光通信、衍射光学和显示领域有着广泛的应用。这项研究报告了含偶氮苯(Azo)液晶嵌段共聚物超分子复合物薄膜中光诱导的光学各向异性,这种复合物在光图案化后可以脱色,形成无色图案双折射聚合物薄膜。这种超分子复合物是通过低分子量偶氮苯酚与由 LC 苯甲酸(PhM)嵌段和聚乙烯吡啶)单元组成的 LC AB 二嵌段和 ABA 三嵌段共聚物宿主之间的分子间吡啶-苯酚氢键作用制备的。在线性偏振光照射下,主聚合物的分子结构和复合物形成的形态模式会影响偶氮基团的取向行为。氢键偶氮基团的光取向伴随着非光致变色 PhM 单元的协同取向,后者形成单独的微相并稳定偶氮基团的取向。这种效应是嵌段共聚物复合物所特有的,而用作参考样品的无规共聚物复合物则不存在这种效应。将嵌段共聚物复合物加热到玻璃转化温度以上,可以放大薄膜中的光学各向异性,随后用二乙醚漂洗,可以制备出无色双折射聚合物薄膜。
期刊介绍:
ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies.
ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.