{"title":"第二代 Zwitterionic Aza-Diarylethene:光可逆 CN 键形成、三态光开关、热能释放和简便的光引发聚合反应","authors":"Henry Dube, Maximilian Sacherer","doi":"10.1002/anie.202415961","DOIUrl":null,"url":null,"abstract":"Diarylethenes are a well-studied and optimized class of photoswitches with a wide range of applications, including data storage, smart materials, or photocontrolled catalysis and biological processes. Most recently, aza-diarylethenes have been developed in which carbon-carbon bond connections are replaced by carbon-nitrogen connections. This structural elaboration opens an entire new structure and property space expanding versatility and applicability of diarylethenes. In this work, we present the second generation of zwitterionic aza-diarylethenes, which finally allows for fully reversible photoswitching and precise control over all three switching states. High-yielding photoswitching between the neutral open form and a zwitterionic Z isomer is achieved with two different wavelengths of light. The third zwitterionic E isomeric state can be reached up to 87% upon irradiation with a third wavelength. Its high energy content of >10 kcal/mol can be released thermally by deliberate solvent change as trigger mechanism, rendering aza-diarylethenes into interesting candidates for molecular solar thermal energy storage (MOST) applications. The third state further serves as locking state, allowing to toggle light-responsiveness reversibly between thermally labile and thermally stable switching. Further, irradiation of the zwitterionic states leads to highly efficient photopolymerization of methyl acrylate (MA), directly harnessing the unleashed chemical reactivity of aza-diarylethene in materials applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":null,"pages":null},"PeriodicalIF":16.1000,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Second Generation Zwitterionic Aza-Diarylethene: Photoreversible CN Bond Formation, Three-State Photoswitching, Thermal Energy Release, and Facile Photoinitiation of Polymerization\",\"authors\":\"Henry Dube, Maximilian Sacherer\",\"doi\":\"10.1002/anie.202415961\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Diarylethenes are a well-studied and optimized class of photoswitches with a wide range of applications, including data storage, smart materials, or photocontrolled catalysis and biological processes. Most recently, aza-diarylethenes have been developed in which carbon-carbon bond connections are replaced by carbon-nitrogen connections. This structural elaboration opens an entire new structure and property space expanding versatility and applicability of diarylethenes. In this work, we present the second generation of zwitterionic aza-diarylethenes, which finally allows for fully reversible photoswitching and precise control over all three switching states. High-yielding photoswitching between the neutral open form and a zwitterionic Z isomer is achieved with two different wavelengths of light. The third zwitterionic E isomeric state can be reached up to 87% upon irradiation with a third wavelength. Its high energy content of >10 kcal/mol can be released thermally by deliberate solvent change as trigger mechanism, rendering aza-diarylethenes into interesting candidates for molecular solar thermal energy storage (MOST) applications. The third state further serves as locking state, allowing to toggle light-responsiveness reversibly between thermally labile and thermally stable switching. 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引用次数: 0
摘要
二月嫂是一类经过充分研究和优化的光开关,具有广泛的应用,包括数据存储、智能材料或光控催化和生物过程。最近,人们开发出了氮杂二元乙烯,碳-碳键连接被碳-氮键连接所取代。这种结构上的改进开辟了一个全新的结构和性质空间,扩大了二元乙烯的多功能性和适用性。在这项工作中,我们展示了第二代氮杂二元乙烯,最终实现了完全可逆的光开关和对所有三种开关状态的精确控制。通过两种不同波长的光,我们实现了中性开放形式和齐聚物 Z 异构体之间的高产光开关。在第三种波长的照射下,第三种齐聚物 E 异构体状态的转换率可达 87%。它的能量含量高达 10 kcal/mol,可以通过故意改变溶剂作为触发机制进行热释放,从而使偶氮二芳香族化合物成为分子太阳能热储(MOST)应用的有趣候选物质。第三种状态还可作为锁定状态,在热易变和热稳定切换之间可逆地切换光响应性。此外,辐照齐聚态可导致丙烯酸甲酯(MA)的高效光聚合,从而在材料应用中直接利用偶氮二芳香族化合物释放的化学反应活性。
Second Generation Zwitterionic Aza-Diarylethene: Photoreversible CN Bond Formation, Three-State Photoswitching, Thermal Energy Release, and Facile Photoinitiation of Polymerization
Diarylethenes are a well-studied and optimized class of photoswitches with a wide range of applications, including data storage, smart materials, or photocontrolled catalysis and biological processes. Most recently, aza-diarylethenes have been developed in which carbon-carbon bond connections are replaced by carbon-nitrogen connections. This structural elaboration opens an entire new structure and property space expanding versatility and applicability of diarylethenes. In this work, we present the second generation of zwitterionic aza-diarylethenes, which finally allows for fully reversible photoswitching and precise control over all three switching states. High-yielding photoswitching between the neutral open form and a zwitterionic Z isomer is achieved with two different wavelengths of light. The third zwitterionic E isomeric state can be reached up to 87% upon irradiation with a third wavelength. Its high energy content of >10 kcal/mol can be released thermally by deliberate solvent change as trigger mechanism, rendering aza-diarylethenes into interesting candidates for molecular solar thermal energy storage (MOST) applications. The third state further serves as locking state, allowing to toggle light-responsiveness reversibly between thermally labile and thermally stable switching. Further, irradiation of the zwitterionic states leads to highly efficient photopolymerization of methyl acrylate (MA), directly harnessing the unleashed chemical reactivity of aza-diarylethene in materials applications.
期刊介绍:
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.