Wang Xinxin, Jin Yucheng, Li Ning, Zhang Hao, Liu Xiaolin, Yang Xiya, Pan Houhe, Wang Tianyu, Wang Kang, Qi Dongdong, Jiang Jianzhuang
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing, 100083, China.
Angew Chem Int Ed Engl. 2024 Apr 8;63(15):e202401014. doi: 10.1002/anie.202401014. Epub 2024 Feb 23.
Developing high connectivity (>8) three-dimensional (3D) covalent organic frameworks (COFs) towards new topologies and functions remains a great challenge owing to the difficulty in getting high connectivity organic building blocks. This however represents the most important step towards promoting the diversity of COFs due to the still limited dynamic covalent bonds available for constructing COFs at this stage. Herein, highly connected phthalocyanine-based (Pc-based) 3D COFs MPc-THHI-COFs (M=H, Ni) were afforded from the reaction between 2,3,9,10,16,17,23,24-octacarboxyphthalocyanine M(TAPc) (M=H, Ni) and 5,5',5'',5''',5'''',5'''''-(triphenylene-2,3,6,7,10,11-hexayl)hexa(isophthalohydrazide) (THHI) with 12 connecting sites. Powder X-ray diffraction analysis together with theoretical simulations and transmission electron microscopy reveals their crystalline nature with an unprecedented non-interpenetrated shp topology. Experimental and theoretical investigations disclose the broadened visible light absorption range and narrow optical band gap of MPc-THHI-COFs. This in combination with their 3D nanochannels endows them with efficient photocatalysis performance for HO generation from O and HO via 2e oxygen reduction reaction and 2e water oxidation reaction under visible-light irradiation (λ >400 nm). This work provides valuable result for the development of high connectivity functional COFs towards diverse application potentials.
由于难以获得高连接性的有机结构单元，开发具有高连接性（>8）的三维（3D）共价有机框架（COF）以实现新的拓扑结构和功能仍然是一个巨大的挑战。然而，这是促进COF多样性的最重要步骤，因为现阶段可用于构建COF的动态共价键仍然有限。在此，通过2,3,9,10,16,17,23,24-八羧基酞菁M（TAPc）（M = H，Ni）与具有12个连接位点的5,5',5'',5''',5'''',5'''''-(亚苯基-2,3,6,7,10,11-六亚基)六(间苯二甲酰肼)(THHI)之间的反应，得到了高连接性的基于酞菁的（Pc基）3D COF MPc-THHI-COF（M = H，Ni）。粉末X射线衍射分析、理论模拟和透射电子显微镜揭示了它们具有前所未有的非互穿shp拓扑结构的晶体性质。实验和理论研究表明，MPc-THHI-COF具有拓宽的可见光吸收范围和窄的光学带隙。这与它们的3D纳米通道相结合，使它们在可见光照射（λ>400 nm）下通过2e氧还原反应和2e水氧化反应从O和HO生成HO具有高效的光催化性能。这项工作为开发具有高连接性的功能性COF以实现多种应用潜力提供了有价值的结果。
