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.本研究通过伸长型四面体连接体与Zr6、Zr8团簇的组装，合成了两种互不穿插的锆基金属有机框架（zirconium metal–organic frameworks, Zr-MOFs）NPF-200与NPF-201。二者为首批具备类β-UH3的4,12,12T1拓扑结构的锆基金属有机框架。经活化处理后，NPF-200在所有由四面体配体合成的锆基金属有机框架中，拥有最高的BET比表面积（5463 m²·g⁻¹）与孔隙体积（81.6%）。NPF-201由带负电的硼中心四面体连接体构筑而成，属于阴离子型锆基金属有机框架，可选择性吸附光活性[Ru(bpy)3]²+，用于硫苯甲醚的多相光氧化反应。