Octanuclear Zinc Clusters in Microporous Organic Polymers: Network‐Enhanced Reductive CO₂ Fixation to Formamides at Room Temperature

A building block containing eight zincs and eight iodo groups (8 Zn) is obtained by the Zn complexation of a salen ligand bearing two additional hydroxy groups. Through the Sonogashira–Hagihara coupling of 8 Zn with 1,3,5,7‐tetra(4‐ethynylphenyl) adamantane, microporous organic polymers bearing octanuclear zinc clusters (MOP‐8 Zn) are prepared, exhibiting a high surface area of 562 m 2 g −1 , microporosity, and a particulate morphology with an average diameter of 249 nm. The MOP‐8 Zn exhibits significantly enhanced catalytic performance, compared to molecular counterparts, in the reductive carbon dioxide fixation to formamides, possibly due to the cooperative adsorption and confinement effect of networks on substrates.