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

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 H₂SO₄) 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.