Changing Metal Sequences in Multivariate Metal-Organic Frameworks via Synthetic Pathway Modulation

Multivariate metal-organic frameworks (MTV MOFs) incorporate various metals and/or linkers within a periodic backbone, offering structural diversity and emergent functionalities.Typically, conventional one-pot synthesis does not allow for any control over the spatial arrangement, or sequencing, of metals within the framework.Here, we present a synthetic strategy to alter metal sequencing in multi-metallic MTV MOFs, yielding materials with identical composition yet distinct local metal arrangements and properties.Using isostructural mCB-Co and mCB-Ni MOFs, we generate two MTV MOFs with different Ni/Co sequences, resulting in distinct semiconducting and magnetic properties.High-resolution electrospray ionization mass spectrometry (ESI-HRMS) reveals the formation of distinct precursor species in solution, suggesting that prenucleation chemistry influences the final metal arrangement.This work establishes a new approach for modulating/altering metal organization in MTV MOFs, enabling tunable functional properties in multi-metallic frameworks for applications in catalysis, electronics, and quantum materials.