Immobilization of a Full Photosystem in the Large‐Pore MIL‐101 Metal–Organic Framework for CO2 reduction

Abstract A molecular catalyst [Cp*Rh(4,4′‐bpydc)] 2+ and a molecular photosensitizer [Ru(bpy) 2 (4,4′‐bpydc)] 2+ (bpydc=bipyridinedicarboxylic acid) were co‐immobilized into the highly porous metal–organic framework MIL‐101‐NH 2 (Al) upon easy postsynthetic impregnation. The Rh–Ru@MIL‐101‐NH 2 composite allows the reduction of CO 2 under visible light, while exhibiting remarkable selectivity with the exclusive production of formate. This Rh–Ru@MIL‐101‐NH 2 solid represents the first example of MOFs functionalized with both a catalyst and a photosensitizer in a noncovalent fashion. Thanks to the coconfinement of the catalyst and photosensitizer into the cavity's nanospace, the MOF pores are used as nanoreactors and enable molecular catalysis in a heterogeneous manner.