Covalent-Coordination-Dual-Driven <i>In Situ</i> Modular Assembly of 12-Connected Nickel-Based Metal–Organic Frameworks

The practical application of metal-organic frameworks (MOFs) is often hindered by the trade-off among structural stability, synthetic complexity, and functional tunability. Herein, we present a facile <i>in situ</i> modular assembly of highly stable 12-connected Ni₈-MOFs by integrating the formation of covalent imine bonds and metal-ligand coordination bonds in a one-pot reaction. This approach utilizes simple precursors of nickel acetate, 4-aminopyrazoles, and diverse aromatic aldehydes to construct a library of 31 highly crystalline Ni₈-MOFs (<b>JNU-230-JNU-260</b>) under traditional refluxing conditions. We further demonstrate the scalability and sustainability of this synthetic strategy, affording gram-scale production per batch using recycled reaction solvents, with no compromise in crystallinity or porosity for at least 3 additional batches. Moreover, <i>in situ</i> modular assembly and donor-acceptor regulation enable the formation of <b>JNU-244</b> as a highly efficient and stable heterogeneous photocatalyst, achieving a yield of up to 99% in a visible-light-driven cross-dehydrogenative coupling reaction with excellent recyclability. This work offers a new platform for the precise and sustainable construction of highly stable, functionally advanced MOFs, highlighting the power of synergistic covalent-coordination-dual driven assembly in materials design.