High-Throughput Discovery of a Rhombohedral Twelve-Connected Zirconium-Based Metal-Organic Framework with Ordered Terephthalate and Fumarate Linkers

We report a metal-organic framework where an ordered array of two linkers with differing length and geometry connect [Zr-6(OH)(4)O-4](12+) clusters into a twelve-connected fcu net that is rhombohedrally distorted from cubic symmetry. The ordered binding of equal numbers of terephthalate and fumarate ditopic carboxylate linkers at the trigonal antiprismatic Zr-6 core creates close-packed layers of fumarate-connected clusters that are connected along the single remaining threefold axis by terephthalates. This well-defined linker arrangement retains the three-dimensional porosity of the Zr cluster-based UiO family while creating two distinct windows within the channels that define two distinct guest diffusion paths. The ordered material is accessed by a restricted combination of composition and process parameters that were identified by high-throughput synthesis.