Heterobimetallic Synergism in Triple‐Redox 2D Framework for Largely Boosted Water Oxidation and Flanked Carboxylic‐Acid‐Triggered Unconventional Tandem Catalysis

Abstract A fish‐bone‐shaped and thermochemically stable 2D metal‐organic framework (MOF) with multimodal active center‐decked pore‐wall is devised. Redox‐active [Co ₂ (COO) ₄ ] node and thiazolo[5,4‐d]thiazole functionalization benefit this mixed‐ligand MOF exhibiting electrochemical water oxidation with 375 mV overpotential at 10 mA cm ⁻² current density and 78 mV per dec Tafel slope in alkaline medium. Pair of oppositely oriented carboxylic acids aids postmetalation with transition metal ions to engineer heterobimetallic materials. Notably, overpotential of Ni ²⁺ grafted triple‐redox composite reduces to 270 mV with twofold declined Tafel slope than the parent MOF, ranking among the best‐reported values, and outperforming majority of related catalysts. Significantly, turnover frequency and charge transfer resistance display 35.5 and 1.4‐fold upsurge, respectively, with much uplifted chronopotentiometric stability and increase active surface area owing to synergistic Co(II)–Ni(II) coupling. The simultaneous presence of ─COOH and nitrogen‐rich moieties renders this hydrogen‐bonded MOF as acid–base synergistic catalyst for recyclable deacetalization‐Knoevenagel reaction with >99% product yield under solvent‐free mild condition. Besides control experiments, unique role of ─COOH as hydrogen‐bond donor site in substrate activation is validated from comparing the performances of molecular‐shearing approach‐derived structurally similar unfunctionalized MOF, and the heterobimetallic composite. To the best of tandem Knoevenagel condensation, larger‐sized acetal exhibits poor yield of α,β‐unsaturated dicyanides, and demonstrates pore‐fitting‐mediated size‐selectivity.