Wang Weitao, Wang Haotian, Tang Xiaohui, Huo Jinlei, Su Yan, Lu Chuangye, Zhang Yujian, Xu Hong, Gu Cheng
State Key Laboratory of Luminescent Materials and Devices, Institute of Polymer Optoelectronic Materials and Devices, South China University of Technology No. 381 Wushan Road, Tianhe District Guangzhou 510640 P. R. China
Department of Chemistry, Zhejiang Normal University Jinhua 321004 P. R. China
Chem Sci. 2022 Jul 9;13(29):8679-8685. doi: 10.1039/d2sc02503e. eCollection 2022 Jul 29.
Designing delocalized excitons with low binding energy ( ) in organic semiconductors is urgently required for efficient photochemistry because the excitons in most organic materials are localized with a high of >300 meV. In this work, we report the achievement of a low of ∼50 meV by constructing phenothiazine-based covalent organic frameworks (COFs) with inherent crystallinity, porosity, chemical robustness, and feasibility of bandgap engineering. The low facilitates effective exciton dissociation and thus promotes photocatalysis by using these COFs. As a demonstration, we subject these COFs to photocatalytic polymerization to synthesize polymers with remarkably high molecular weight without any requirement of the metal catalyst. Our results can facilitate the rational design of porous materials with low for efficient photocatalysis.
由于大多数有机材料中的激子是局域化的，其束缚能高达300meV以上，因此迫切需要在有机半导体中设计具有低束缚能（ ）的离域激子以实现高效光化学。在这项工作中，我们报告了通过构建具有固有结晶度、孔隙率、化学稳定性和带隙工程可行性的吩噻嗪基共价有机框架（COF），实现了约50meV的低束缚能。这种低束缚能有助于激子的有效解离，从而通过使用这些COF促进光催化。作为一个例证，我们将这些COF用于光催化聚合反应，以合成具有极高分子量的聚合物，而无需任何金属催化剂。我们的结果有助于合理设计具有低束缚能的多孔材料以实现高效光催化。
