Robust dioxin-linked metallophthalocyanine tbo topology covalent organic frameworks and their photocatalytic properties.

Constructing 3D functional covalent organic frameworks (COFs) with both robust linkage and planar macrocycle building blocks still remains a challenge due to the difficulty in adjusting both the crystallinity and the dominant 2D structures. In addition, it is also challenging to selectively convert inert C(sp³)-H bonds into value-added chemicals. Herein, robust 3D COFs, USTB-28-M (M=Co, Ni, Cu), have been polymerized from the nucleophilic aromatic substitution reaction of D _3h-symmetric 2,3,6,7,14,15-hexahydroxyltriptycene with D _4h-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-Emmett-Teller surface areas of ≤1477 m² g^-1. In particular, the multiple polyhedron subunits in USTB-28-M 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)-H bond into various ketones. Among the three investigated COFs, the USTB-28-Co radical initiator exhibits the best photocatalytic oxidation activity, converting ethylbenzene into acetophenone with a turnover frequency of 63 h^-1, which is much higher than those of the monomer CoPcF₁₆ (8 h^-1) and 2D dioxin-linked counterparts (13 h^-1). This is due to the much prolonged lifetime of the excited state for USTB-28-Co 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.