Programmable Atomic Composition through Transmetalation for Isostructural Multimetallic Metal–Organic Frameworks

Heterometallic metal–organic frameworks (MOFs) offer properties unachievable in monometallic systems, yet their rational synthesis remains limited by thermodynamic biases that favor a narrow set of inorganic node geometries. Here, we report a generalizable post-synthetic strategy to construct isostructural multimetallic MOFs through controlled transmetalation of NU-3001. We incorporate metals spanning distinct regions of the periodic table, including transition metals (Fe, Zr), lanthanides (Ho), and actinides (Th). Comprehensive characterization confirms uniform metal incorporation while preserving the parent MOF topology, crystallinity, and porosity. Time-dependent studies reveal metal-dependent exchange preferences; variable-temperature diffraction and sorption measurements demonstrate comparable thermal stability across derivatives, with some maintaining crystallinity up to 450 °C and porosity up to 300 °C. We show that analogous materials cannot be accessed through de novo synthesis methods, underscoring the essential role of transmetalation in overcoming thermodynamic preferences. This work establishes NU-3001 as a versatile platform for constructing compositionally programmable multimetallic MOFs.