Li Chunyang, Zhang Guoqun, Xu He, Wei Linjing, Liu Wuhua, Zhang Kaiwei, Wang Bingnan, Wang Chengliang, Qin Anjun, Tang Ben Zhong
State Key Laboratory of Luminescent Materials and Devices, Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, Center for Aggregation-Induced Emission, South China University of Technology Guangzhou 510640 China
School of Integrated Circuits, State Key Laboratory of New Textile Materials and Advanced Processing, Key Laboratory of Material Chemistry for Energy Conversion and Storage (Ministry of Education), Huazhong University of Science and Technology Wuhan 430074 China
Chem Sci. 2025 Aug 19. doi: 10.1039/d5sc03991f.
The p-π conjugated polymers have garnered considerable interest owing to their distinctive electronic structures, which arise from the interaction between p orbitals and π electrons. Currently, the p-π conjugated polymers with charged side chains have been extensively studied, those featuring charged backbones are rare due to the synthetic difficulties. In this work, we developed a spontaneous amino-yne click polymerization utilizing pyridinium-activated alkyne and aromatic primary amine monomers, enabling the efficient synthesis of p-π conjugated ionic polymers with high weight-average molecular weights ( , up to 44 100) and excellent yields (up to 98%). The resultant polymers are emissive, but demonstrate remarkable photothermal properties. Upon irradiation with an 808 nm laser (1.0 W cm), the polymer powders rapidly reach temperatures as high as 310 °C within 20 s, the highest reported value for polymeric photothermal materials while maintaining outstanding photostability. Additionally, these polymers function as effective electrode materials a four-electron-transfer process, retaining 85.2% of their capacity after 100 charge-discharge cycles. This work not only establishes a novel pyridinium-activated alkyne-based spontaneous amino-yne click polymerization but also provides a versatile strategy for designing p-π conjugated ionic polymers with broad application potentials.
p-π共轭聚合物因其独特的电子结构而备受关注，这种结构源于p轨道与π电子之间的相互作用。目前，带有带电侧链的p-π共轭聚合物已得到广泛研究，而具有带电主链的聚合物由于合成困难而较为罕见。在这项工作中，我们利用吡啶鎓活化的炔烃和芳香伯胺单体开发了一种自发的氨基-炔点击聚合反应，能够高效合成具有高重均分子量（高达44 100）和优异产率（高达98%）的p-π共轭离子聚合物。所得聚合物具有发光性，但同时表现出显著的光热性能。在用808 nm激光（1.0 W cm）照射时，聚合物粉末在20 s内迅速升温至高达310 °C，这是聚合物光热材料报道的最高值，同时保持了出色的光稳定性。此外，这些聚合物作为有效的电极材料，在四电子转移过程中，经过100次充放电循环后仍保留其容量的85.2%。这项工作不仅建立了一种基于吡啶鎓活化炔烃的新型自发氨基-炔点击聚合反应，还为设计具有广泛应用潜力的p-π共轭离子聚合物提供了一种通用策略。
