Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization

Atomistic control of the coordination environment of lattice ions and the distribution of metal sites within crystalline mixed-metal coordination polymers remain significant synthetic challenges. Herein is reported the mechanochemical synthesis of a reticular family of crystalline heterobimetallic metal-organic frameworks (MOFs) is now achieved by polymerization of molecular Ru₂ [II,III] complexes, featuring unprotected carboxylic acid substituents, with Cu(OAc)₂ . The resulting crystalline heterobimetallic MOFs are solid solutions of Ru₂ and Cu₂ sites housed within [M₃ L₂ ] phases. The developed mechanochemical strategy is modular and allows for systematic control of the primary coordination sphere of the Ru₂ sites within an isoreticular family of materials. This strategy is anticipated to provide a rational approach to atomically precise mixed-metal materials.