Antagonistically Functionalized Cobalt‐Organic Framework Enabling Bifunctional Water Splitting and One‐Pot Synthesis of Bioactive 4H‐Pyrans via Synergistic Catalysis

ABSTRACT The rational construction of multifunctional metal–organic frameworks (MOFs) integrating redox and acid‐base cooperativity offers a transformative platform for sustainable energy and green chemical synthesis. We report here a structurally undulated robust Co(II)‐framework that encompasses open metal sites (OMS) and carboxamide moieties. The activated framework exhibits superior overpotentials of 262 mV for oxygen evolution reaction (OER, 1 M KOH) and 154 mV for hydrogen evolution reaction (HER, 0.5 M H 2 SO 4 ) at 10 mA cm − 2 than the majority of contemporary and benchmark catalysts, accompanied by remarkable Tafel slopes of 60.7 and 114.06 mV dec − 1 , respectively. Besides impressive intrinsic electrocatalytic parameters, 2000 cycles of durability and >30 h chronoamperometric stability underscore its structural resilience in bifunctional electrocatalysis. Building on an incisive juxtaposition of antagonistic functionality, the MOF catalyzes one‐pot, three‐component Knoevenagel‐Michael condensation, producing a vast range of 2‐amino‐3‐cyano‐4H‐pyrans, including four pharmacologically active anticancer and antibacterial molecules in quantitative yields under mild‐condition. Notably, the reaction exhibits molecular‐dimension‐mediated size selectivity, revealing cooperative acid‐base interplay‐induced pore‐confined catalysis. Control experiments and density‐functional‐theory studies corroborate the synergistic participation of OMS and HBD groups. This study introduces a unified design strategy for bi‐functional MOF that bridges high‐performance renewable energy conversion and green organic synthesis through synergistic involvement of pore‐embedded antagonistic functionality.