Host–Guest Interactions in a Metal–Organic Framework Isoreticular Series for Molecular Photocatalytic CO(2) Reduction

A strategy to improve homogeneous molecular catalyst stability, efficiency, and selectivity is the immobilization on supporting surfaces or within host matrices. Herein, we examine the co‐immobilization of a CO(2) reduction catalyst [ReBr(CO)(3)(4,4′‐dcbpy)] and a photosensitizer [Ru(bpy)(2)(5,5′‐dcbpy)]Cl(2) using the isoreticular series of metal–organic frameworks (MOFs) UiO‐66, ‐67, and ‐68. Specific host pore size choice enables distinct catalyst and photosensitizer spatial location—either at the outer MOF particle surface or inside the MOF cavities—affecting catalyst stability, electronic communication between reaction center and photosensitizer, and consequently the apparent catalytic rates. These results allow for a rational understanding of an optimized supramolecular layout of catalyst, photosensitizer, and host matrix.