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A -symmetric hexatopic monomer was first prepared by attaching the three-fold ditopic moiety 2,6-dimethylpyridine to the -positions of a phenyl ring. It was further condensed at its six pyridylmethyl carbons with linear ditopic aromatic dialdehydes, resulting in two vinylene-linked COFs with heteroporous topologies, as revealed by powder X-ray diffraction (PXRD), nitrogen sorption, and pore-size distribution analyses, as well as transmission electron microscopy (TEM) image. The linear- and cross-conjugations, respectively, arising from the 2,6-linked pyridines and -linked phenylenes in the hexatopic nodes rendered the resultant COFs with well-patterned π-delocalization, allowing for efficiently catalyzing the bromination of aromatic derivatives with the pore-size-dependent conversion yields and regioselectivity under the irradiation of green light.
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http://dx.doi.org/10.1021/jacs.3c04410 | DOI Listing |
Angew Chem Int Ed Engl
August 2025
Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi, 214122, P.R. China.
The limited design strategy of three-dimensional covalent organic frameworks (3D COFs) greatly restricts their structural diversification and potential applications. Herein, we propose an inwardly directed linker propagation strategy for the targeted assembly of 3D COFs (COF-IN-1 and COF-IN-2) and compare them with outwardly directed expanded COFs (COF-OUT-1 and COF-OUT-2). COF-OUTs exhibit planar heteroporous 2D frameworks with cpt topology, while COF-INs engineer controlled triple entanglements into networks, forming 3D frameworks with acs topology.
View Article and Find Full Text PDFJ Am Chem Soc
August 2023
School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China.
A -symmetric hexatopic monomer was first prepared by attaching the three-fold ditopic moiety 2,6-dimethylpyridine to the -positions of a phenyl ring. It was further condensed at its six pyridylmethyl carbons with linear ditopic aromatic dialdehydes, resulting in two vinylene-linked COFs with heteroporous topologies, as revealed by powder X-ray diffraction (PXRD), nitrogen sorption, and pore-size distribution analyses, as well as transmission electron microscopy (TEM) image. The linear- and cross-conjugations, respectively, arising from the 2,6-linked pyridines and -linked phenylenes in the hexatopic nodes rendered the resultant COFs with well-patterned π-delocalization, allowing for efficiently catalyzing the bromination of aromatic derivatives with the pore-size-dependent conversion yields and regioselectivity under the irradiation of green light.
View Article and Find Full Text PDFMacromol Rapid Commun
June 2023
Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Science, Tianjin University, Tianjin, 300072, P. R. China.
Covalent organic frameworks (COFs) have attracted increasing research interest due to their intriguing topological structures and fascinating properties. Diverse COFs with different shapes and sizes are developed by the design of appropriate building blocks. However, the heteroporous COFs to date are still in their infancy due to the relatively limited configuration of precursors.
View Article and Find Full Text PDFChem Soc Rev
June 2020
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional Molecules, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China. xzhao@si
Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers assembled by connecting organic building units via covalent bonds. They are characterized as extended two-dimensional (2D) or three-dimensional (3D) frameworks with precise spatial structures and building block distribution. A key feature of COFs is their inherent porosity originating from their well-ordered nanopores which are designable, tunable and modifiable through pore engineering.
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