Proximity-Enabled Photochemical C-H Functionalization using a Covalent Organic Framework-Confined Fe₂^IV-μ-oxo Species...

Water has been recognized as an excellent solvent for maneuvering both the catalytic activity and selectivity, especially in the case of heterogeneous catalysis. However, maintaining the active catalytic species in their higher oxidation states (IV/V) while retaining the catalytic activity and recyclability in water is an enormous challenge. Herein, we have developed a solution to this problem using covalent organic frameworks (COFs) to immobilize the (Et₄N)₂[Fe^III(Cl)bTAML] molecules, taking advantage of the COF's morphology and surface charge. By using the visible light and [Co^III(NH₃)₅Cl]Cl₂ as a sacrificial electron acceptor within the COF, we have successfully generated and stabilized the [(bTAML)Fe^IV-O-Fe^IV(bTAML)]^- species in water. The COF backbone simultaneously acts as a porous host and a photosensitizer. This is the first time that the photochemically generated Fe₂^IV-μ-oxo radical cation species has demonstrated high catalytic activity with moderate to high yield for the selective oxidation of the unactivated C-H bonds, even in water. To enhance the catalytic activity and achieve good recyclability, we have developed a TpDPP COF film by transforming the TpDPP COF nanospheres. We have achieved the regio- and stereoselective functionalization of unactivated C-H bonds of alkanes and alkenes (3°:2° = 102:1 for adamantane with the COF film), which is improbable in homogeneous conditions. The film exhibits C-H bond oxidation with higher catalytic yield (32-98%) and a higher degree of selectivity (cis/trans = 74:1; 3°:2° = 100:1 for cis-decalin).