Photosensitizing Metal-Organic Layers for Efficient Sunlight-Driven Carbon Dioxide Reduction.

Metal-organic layers (MOLs), a free-standing monolayer version of two-dimensional metal-organic frameworks (MOFs), have emerged as a new class of 2D materials for many potential applications. Here we report the design of a new photosensitizing MOL, Hf-Ru, based on Hf secondary building units (SBUs) and [Ru(bpy)] (bpy = 2,2'-bipyridine) derived dicarboxylate ligands. After modifying the SBU surface of Hf-Ru with M(bpy)(CO)X (M = Re and X = Cl or M = Mn and X = Br) derived capping molecules through carboxylate exchange reactions, the resultant Hf-Ru-Re and Hf-Ru-Mn MOLs possess both [Ru(bpy)] photosensitizers and M(bpy)(CO)X catalysts for efficient photocatalytic CO reduction. The proximity of the MOL skeleton to the capping ligands (1-2 nm) facilitates electron transfer from the reduced photosensitizer [Ru(bpy)] to M(bpy)(CO)X (M = Re, Mn) catalytic centers, resulting in CO reduction turnover numbers of 8613 under artificial visible light and of 670 under sunlight. MOLs thus represent a novel platform to assemble multifunctional materials for studying artificial photosynthesis.