Abstractπ‐Conjugated aromatic polymers (πCAPs) are central components of functional materials yet suffer from insolubility without multiple covalent substituents on their backbones. We herein disclose a new strategy for the facile processing of unsubstituted heterocyclic πCAPs (i.e., poly(para‐phenylene‐2,6‐benzobisoxazole) and poly(benzimidazobenzo‐phenanthroline)), independent of the polymer length, via non‐covalent encircling with aromatic micelles, composed of bent aromatic amphiphiles, in water. The UV/Visible studies reveal that the efficiencies of the present encircling method are ≈10 to 50‐fold higher than those using conventional amphiphiles under the same conditions. The AFM and SEM analyses of the resultant aqueous polymer composites show that otherwise insoluble πCAPs form fine bundles (e.g., ≈1 nm in thickness) in the tubular aromatic micelles, through efficient π‐stacking interactions. In the same way, pristine poly(para‐phenylene) can be dissolved in water, displaying enhanced fluorescence (10‐fold), relative to the polymer solid. Two types of unsubstituted πCAPs are likewise co‐encircled in water, indicated by UV/Visible analysis. Importantly, aqueous processing of the encircled πCAPs into free‐standing single‐ or multicomponent films with submicrometer thickness is demonstrated through a simple filtration‐annealing protocol.
摘要π-共轭芳香族聚合物(πCAPs)是功能材料的核心成分,但如果其骨架上没有多个共价取代基,就会出现不溶解的问题。我们在此揭示了一种新策略,即在
水中通过与由弯曲的芳香族两性化合物组成的芳香族胶束进行非共价包覆,轻松加工未取代的杂环πCAP(即聚(对位亚苯基-2,6-苯并
异恶唑)和聚(
苯并咪唑偶氮
菲咯啉)),而不受聚合物长度的影响。紫外/可见光研究表明,在相同条件下,本环绕方法的效率比使用传统双亲化合物的方法高出≈10 至 50 倍。对由此产生的
水性聚合物复合材料进行的原子力显微镜和扫描电子显微镜分析表明,通过有效的π堆叠相互作用,原本不溶于
水的πCAP在管状芳香族胶束中形成了细束(例如厚度≈1 nm)。同样,原始聚
对苯二甲酸丁二酯可溶解于
水,相对于聚合物固体,其荧光增强(10 倍)。紫外线/可见光分析表明,两种未取代的 πCAP 在
水中同样具有共包覆性。重要的是,通过一个简单的过滤-退火方案,证明了在
水中可将包覆的 πCAP 加工成具有亚微米厚度的独立单组分或多组分薄膜。