Diversification of Conjugated Polymers via Postpolymerization Nucleophilic Aromatic Substitution Reactions with Sulfur-, Oxygen-, and Nitrogen-Based Nucleophiles
Diversification of Conjugated Polymers via Postpolymerization Nucleophilic Aromatic Substitution Reactions with Sulfur-, Oxygen-, and Nitrogen-Based Nucleophiles
复制标题
通过与硫基、氧基和氮基亲核试剂发生后聚合亲核芳香族取代反应实现共轭聚合物的多样化
DOI：
10.1021/acs.macromol.0c02395
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发表时间：
2021
期刊：
影响因子：
5.5
通讯作者：
Inagi Shinsuke
中科院分区：
文献类型：
--
作者：
Shida Naoki;Ninomiya Kazuyuki;Takigawa Natsuki;Imato Keiichi;Ooyama Yousuke;Tomita Ikuyoshi;Inagi Shinsuke
聚合后亲核芳族取代反应被用作有效地使共轭聚合物多样化的策略。共轭聚合物和小分子模型轴承四氟苯基和八氟联苯单元与苯硫酚衍生物，苯酚衍生物，和咔唑在碱的存在下反应。模型反应提供了对反应性、取代的数量和模式、结构特征和光谱数据的见解。苯硫酚衍生物和咔唑在聚合物和模型反应中都实现了氟原子的完全取代，而苯酚衍生物则在每个芳烃环上实现了对位选择性的双取代。高度扭曲和结构刚性的主链结构被确认为一个完全取代的芳烃基序在聚合物和模型，导致形成ofsyn-和anti-atropisomer或轴向手性和扭曲的分子内电荷转移字符。所得到的聚合物和模型显示出独特的光学和电化学性质，包括含硫材料在低温下的磷光。
A postpolymerization nucleophilic aromatic substitution reaction is used as a strategy to efficiently diversify conjugated polymers. Conjugated polymers and small molecular models bearing tetrafluorophenyl and octafluorobiphenyl units are reacted with thiophenol derivatives, phenol derivatives, and carbazole in the presence of bases. Model reactions provide insights into the reactivity, numbers and patterns of substitution, structural features, and spectroscopic data. Thiophenol derivatives and carbazole achieve complete substitution of fluorine atoms in both the polymer and the model reactions, whereas phenol derivatives result in di-substitution in each arene ring withpara-selectivity. The highly twisted and structurally rigid main chain structures are confirmed for a fully substituted arene motif in both the polymers and the models, resulting in the formation ofsyn- andanti-atropisomer or axial chirality and in the twisted intramolecular charge transfer character. The obtained polymers and models show unique optical and electrochemical properties, including phosphorescence at low temperatures in the case of the sulfur-containing materials.