Dimensional Control in Hexanuclear Copper‐Oxo Clusters: From Discrete Molecules to 1D Chains and Their Divergent Catalysis in CO ₂ Cycloaddition

Metal‐oxo clusters are promising for catalysis, yet precise dimensional control over isonuclear clusters remains rarely reported. Herein, the dimensional regulation of two isonuclear hexanuclear copper‐oxo clusters with an identical {Cu 6 ( μ 4 ‐O) 2 } core is achieved, yielding a one‐dimensional chain compound, (NMe 2 H 2 ) 4 [Cu 6 ( μ 4 ‐O) 2 (SO 4 ) 6 (DMF) 2 ] ( 1 ), and a zero‐dimensional discrete compound, [Cu 6 ( μ 4 ‐O) 2 (SO 4 ) 4 (DMSO) 6 (DMF)] ( 2 ). In the catalytic cycloaddition of CO 2 with epoxides, the 1D structure (1) exhibits superior activity and faster kinetics. This enhancement is likely attributable to the dimethylammonium cations in 1 , which facilitate the mass transport of ionic intermediates. This work not only achieves precise dimensional control over isonuclear clusters but also offers new insights into how molecular packing and ionic environments regulate catalytic performance.