Highly Porous Zirconium Metal–Organic Frameworks with β‑UH3‑like Topology Based on Elongated Tetrahedral Linkers

Two non-interpenetrated zirconium metal–organic frameworks (Zr-MOFs), NPF-200 and NPF-201, were synthesized via the assembly of elongated tetrahedral linkers with Zr6 and Zr8 clusters. They represent the first examples of MOFs to have the β-UH3-like, 4,12,12T1 topology. Upon activation, NPF-200 exhibits the largest BET surface area (5463 m2 g–1) and void volume (81.6%) among all MOFs formed from tetrahedral ligands. Composed of negative-charged boron-centered tetrahedral linkers, NPF-201 is an anionic Zr-MOF which selectively uptakes photoactive [Ru­(bpy)3]2+ for heterogeneous photo-oxidation of thioanisole.