Dual Cofactor Co‐Decorated Covalent Organic Framework as an Electron Transfer Regulator for Biomimetic Dioxygen Activation

Abstract Mimicking the synergy of multiple active sites of oxygenase to achieve selective O2 activation for various oxidations is a very challenging but meaningful task. By introducing the reduced nicotinamide adenine dinucleotide (NADH) active site dihydropyridine amido (DHPA) moiety and heme, a dual cofactor co‐decorated covalent organic framework (COF) was obtained to duplicate the synergistically catalytic function of the cytochrome P450 for biomimetic O2 activation. Covalent co‐decoration of dual cofactors in COFs ensures the rapid photogenerated electron transfer from DHPA to heme FeIII to generate FeII, selectively activating O2 to form FeIII−O2•− resembling the cytochrome P450 for improving the performance of alcohol oxidation, avoiding conventionally complex multistep cofactor shuttling and regeneration. Control experiments of a COF analogue containing heme but not DHPA suggested that this dual cofactor construction strategy renders COFs excellent activity and selectivity for O2 activation. As far as we know, this represents the first case of introducing dual cofactor into COFs to echo the cytochrome P450. The well‐defined structural characters and the finely modified bioactive properties open a new avenue to develop novel COFs, which not only augment the diversity of the COF family but also broaden the application of COFs in the field of biomimetic catalysis.