Cyclophanediene and Cyclophanetriene‐Based Conjugated Polymers
Cyclophanediene and Cyclophanetriene‐Based Conjugated Polymers
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基于环芳二烯和环芳三烯的共轭聚合物
DOI：
10.1002/macp.202200397
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发表时间：
2022
影响因子：
2.5
通讯作者：
Weck, Marcus
中科院分区：
文献类型：
--
作者：
Mann, Arielle;Hannigan, Matthew D.;Weck, Marcus
聚（对亚苯基亚乙烯基）（PPV）和聚（亚芳基亚乙烯基）是从有机发光二极管到荧光光学探针等多种应用的关键材料。然而，它们的合成受到非活性或逐步增长聚合技术的阻碍。官能团耐受的烯烃复分解催化剂的开发使得能够使用环烷单体的活性开环复分解聚合（ROMP）以活性方式产生PPV和聚（对亚苯基-共亚芳基亚乙烯基）。低分散性和可溶性 PPV 可以控制重复单元的数量，并且可以在其头部或尾部轻松掺入不同的端基。在这篇综述中，全面概述了含有[2.2]对环芳烷-1,9-二烯、[2.2]间对环芳烷-1,9-二烯、[2.2.2]对环芳烷-1,9,17-三烯和[2.2.2]对环芳烷-1,9,17-三烯的四取代和二取代烷基和烷氧基。 提供苯并噻二唑-[2.2]对环芳烷-1,9-二烯。这些单体的高环应变使得能够与钌引发剂进行有效的聚合。特别强调的是[2.2]对环芳-1,9-二烯，因为它是自 30 年前首次报道以来研究最多的一类聚合环芳二烯。此外，还研究了 ROMP 合成的软材料的应用，重点介绍了易于获取的 PPV 共聚物和可光触发的 PPV 嵌段共聚物，以及在其末端安装超分子识别单元以提供正交自组装结构的 PPV。
Poly(p‐phenylene vinylene)s (PPVs) and poly(arylene vinylene)s are key materials for a variety of applications ranging from organic light emitting diodes to fluorescent optical probes. Their syntheses, however, have been hampered by non‐living or step‐growth polymerization techniques. The development of functional‐group tolerant olefin metathesis catalysts has enabled the use of living ring‐opening metathesis polymerization (ROMP) of cyclophane monomers yielding PPVs and poly(p‐phenylene‐co‐arylene vinylene)s in a living manner. Low dispersity and soluble PPVs are afforded with control over the number of repeat units with easy incorporation of different end‐groups at their heads or tails. In this review, a comprehensive overview of tetrasubstituted and disubstituted alkyl and alkoxy containing [2.2]paracyclophane‐1,9‐diene, [2.2]metaparacyclophane‐1,9‐diene, [2.2.2]paracyclophane‐1,9,17‐triene, and benzothiadiazole‐[2.2]paracyclophane‐1,9‐diene is provided. The high ring strain of these monomers enables efficient polymerizations with ruthenium initiators. A particular emphasis is on [2.2]paracyclophane‐1,9‐dienes as it is the most investigated class of polymerized cyclophanediene since initially reported 30 years ago. Additionally, applications for soft materials synthesized by ROMP are examined, highlighting easily accessed PPV copolymers and PPV block copolymers that can be phototriggered, as well as PPVs featuring supramolecular recognition units installed at their termini to afford orthogonally self‐assembled architectures.