Building Co₁₆-N₃-Based UiO-MOF to Expand Design Parameters for MOF Photosensitization

The construction of secondary building units (SBUs) in versatile metal-organic frameworks (MOFs) represents a promising method for developing multi-functional materials, especially for improving their sensitizing ability. Herein, we developed a dual small molecules auxiliary strategy to construct a high-nuclear transition-metal-based UiO-architecture Co₁₆-MOF-BDC with visible-light-absorbing capacity. Remarkably, the N₃ ^- molecule in hexadecameric cobalt azide SBU offers novel modification sites to precise bonding of strong visible-light-absorbing chromophores via click reaction. The resulting Bodipy@Co₁₆-MOF-BDC exhibits extremely high performance for oxidative coupling benzylamine (~100 % yield) via both energy and electron transfer processes, which is much superior to that of Co₁₆-MOF-BDC (31.5 %) and Carboxyl @Co₁₆-MOF-BDC (37.5 %). Systematic investigations reveal that the advantages of Bodipy@Co₁₆-MOF-BDC in dual light-absorbing channels, robust bonding between Bodipy/Co₁₆ clusters and efficient electron-hole separation can greatly boost photosynthesis. This work provides an ideal molecular platform for synergy between photosensitizing MOFs and chromophores by constructing high-nuclear transition-metal-based SBUs with surface-modifiable small molecules.