A Porphyrin-Faced Zn 8 L 6 Cage for Selective Oxidation of C(sp 3 )-H Bonds and Sulfides.

Catalytic oxidation of benzyl C-H bonds and sulfides from fuel oils stands as an attractive proposition in the quest for clean energy, yet their simultaneous oxidation with a singular, economically friendly catalyst is not well established. In this work, the combination of a cobalt(II) porphyrin ligand with 2-pyridinecarboxaldehyde and Zn II yielded a Zn 8 L 6 cage (Co cube). The three-dimensional conjugated structure effectively enhances energy transfer efficiency, enabling the Co cube to show a good ability to activate oxygen under light conditions for photooxidation. Moreover, this catalytic system demonstrates high selectivity for the photocatalytic oxidation of C(sp 3 )-H bonds and sulfides, employing the Co cube as a single component catalyst, molecular oxygen as the oxidant, and activating oxygen into 1 O 2 under mild reaction conditions. This provides significant insights for organic synthesis and future design of photocatalysts with complex molecular components.