Pore-Engineering of Single-Site Ti(IV) Embedded Zr-MOFs for Enhanced Catalytic Hydroboration of Large-Size Carbonyl Substrates

• • Pore size modulation from 9.04 Å to 11.18 Å in microporous Ti(IV)-embedded Zr-MOFs increased catalytic efficiency for hydroboration of carbonyl substrates, but remained suboptimal for larger substrates, highlighting diffusion limitations. • • Linker installation of linear dicarboxylate ligands chelating single-site Ti(IV) into mesoporous Zr-MOFs yielded catalysts with pore size ~21.73 Å, achieving superior catalytic efficiency exceeding 90% for all tested substrates, including large-size carbonyl compounds. • • The mesoporous catalyst preserved inherent mesoporosity, ensuring enhanced mass transfer and accessibility to active sites, which is critical for industrial-scale hydroboration of bulky substrates. • • The study provides a systematic pore-engineering strategy for MOF-based catalysts, demonstrating that precise pore size control and linker installation can overcome diffusion bottlenecks, offering a blueprint for designing efficient heterogeneous catalysts for bulky molecule transformations.