Photosensitizing metal covalent organic framework with fast charge transfer dynamics for efficient CO photoreduction.

Designing artificial photocatalysts for CO reduction is challenging, mainly due to the intrinsic difficulty of making multiple functional units cooperate efficiently. Herein, three-dimensional metal covalent organic frameworks (3D MCOFs) were employed as an innovative platform to integrate a strong Ru(ii) light-harvesting unit, an active Re(i) catalytic center, and an efficient charge separation configuration for photocatalysis. The photosensitive moiety was precisely stabilized into the covalent skeleton by using a rational-designed Ru(ii) complex as one of the building units, while the Re(i) center was linked a shared bridging ligand with an Ru(ii) center, opening an effective pathway for their electronic interaction.