Herein, taking inspirations from metalloenzymes, we constructed atomically dispersed manganese sites anchored onto conjugated tri-s-triazine units of graphitic carbon nitride as a bioinspired photocatalyst (Mn 1 /tri-CN) for the oxo-dehydrogenation of N-heterocycles. The primary coordination sphere of atomic Mn-N 2 sites (role i: oxygen activation) as well as the π−π stacking interactions between tri-s-triazine units and substrate mimicking the secondary coordination sphere (role ii: substrate adsorption) synergistically realized high-efficiency electron transfer/utilization in photocatalytic oxidation reactions, as was demonstrated experimentally and theoretically. The Mn 1 /tri-CN catalyst exhibited impressive oxo-dehydrogenation activity and selectivity toward a broad scope of N-heterocycles in an air atmosphere. The current work suggests that simultaneously engineering the metal active sites of catalysts and the adaptive local environment of the matrix may open an avenue for the synthesis of fine chemicals.

Deterium-labeled (hetero)­aryl bromide is one of the most widespread applicable motifs to achieve important deuterated architectures for various scientific applications. Traditionally, these deterium-labeled (hetero)­aryl bromides are commonly prepared via multistep syntheses. Herein, we disclose a direct H/D exchange protocol for deuteration of (hetero)­aryl bromides using Ag2CO3 as catalyst and D2O as deuterium source. This protocol is highly efficient, simply manipulated, and appliable for deuterium-labeling of over 55 (hetero)­aryl bromides including bioactive druglike molecules and key intermediates of functional materials. In addition, this method showed distinguishing site-selectivity toward the existing transition-metal-catalyzed HIE process, leading to multideuterated (hetero)­aryl bromides in one step.

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