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In addition, it is also challenging to selectively convert inert C(sp3)\u2013H bonds into value-added chemicals. Herein, robust 3D COFs, USTB-28\u2013M (M=Co, Ni, Cu), have been polymerized from the nucleophilic aromatic substitution reaction of D3h-symmetric 2,3,6,7,14,15-hexahydroxyltriptycene with D4h-symmetric hexadecafluorophthalocyanine (MPcF16) under solvothermal conditions. These chemically stable dioxin-linked COFs show isostructural tbo topology made up of three kinds of polyhedron subunits, exhibiting high Brunauer\u2212Emmett\u2212Teller surface areas of \u22641477 m2 g\u22121. In particular, the multiple polyhedron subunits in USTB-28\u2013M could trap N-hydroxyphthalimide at their corners for easily forming stable phthalimide-N-oxyl radicals under visible-light irradiation. The generated radicals efficiently promote the aerobic oxidation of alkyl benzenes with an inert C(sp3)\u2013H bond into various ketones. Among the three investigated COFs, the USTB-28\u2013Co radical initiator exhibits the best photocatalytic oxidation activity, converting ethylbenzene into acetophenone with a turnover frequency of 63 h\u22121, which is much higher than those of the monomer CoPcF16 (8 h\u22121) and 2D dioxin-linked counterparts (13 h\u22121). This is due to the much prolonged lifetime of the excited state for USTB-28\u2013Co based on the femtosecond transient absorption result. The present work not only presents 3D functional COFs with robust connection and permanent porosity, but also illustrates the uniqueness of porous structures of 3D COFs for high-performance photocatalysis.<\/jats:p>","DOI":"10.1093\/nsr\/nwae396","type":"journal-article","created":{"date-parts":[[2024,11,4]],"date-time":"2024-11-04T15:23:54Z","timestamp":1730733834000},"source":"Crossref","is-referenced-by-count":16,"title":["Robust dioxin-linked metallophthalocyanine tbo topology covalent organic frameworks and their photocatalytic properties"],"prefix":"10.1093","volume":"12","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7008-4938","authenticated-orcid":false,"given":"Yucheng","family":"Jin","sequence":"first","affiliation":[{"name":"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 , 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