Programmable Topology in New Families of Heterobimetallic Metal–Organic Frameworks

Using diverse building blocks, such as different heterometallic clusters, in metal–organic framework (MOF) syntheses greatly increases MOF complexity and leads to emergent synergistic properties. However, applying reticular chemistry to syntheses involving more than two molecular building blocks is challenging and there is limited progress in this area. We are therefore motivated to develop a strategy for achieving systematic and differential control over the coordination of multiple metals in MOFs. Herein, we report the design and synthesis of a diverse series of heterobimetallic MOFs with different metal ions and clusters severally distributed throughout two or three inorganic secondary building units (SBUs). By taking advantage of the bifunctional isonicotinate linker and its derivatives, which can coordinatively distinguish between early and late transition metals, we control the assembly and topology of up to three different inorganic SBUs in one-pot solvothermal reactions. Specifically, M₆(μ₃-O)_n(μ₃-OH)_8–n(CO₂)₁₂ (M = Zr⁴⁺, Hf⁴⁺, Dy³⁺) SBUs are formed along with metal-pyridyl complexes. By controlling the geometry of the metal-pyridyl complexes, we direct the overall topology to produce eight new MOFs with fcu, ftw, and previously unreported trinodal pfm crystallographic nets.