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ChemRXiv submission.pdf (589.08 kB)
Atomically Precise Crystalline Materials Based on Kinetically Inert Metal Ions via Reticular Mechanopolymerization
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submitted on 20.02.2020 and posted on 21.02.2020by Wen-Yang Gao, Aishanee Sur, Chen-Hao Wang, Gregory R. Lorzing, Alexandra M. Antonio, Andrew A. Ezazi, Nattamai Bhuvanesh, Eric D. Bloch, David Powers
The incorporation of kinetically inert metal ions as structural elements in crystalline coordination polymers is a synthetic challenge. While a small family of materials based on inert ions has been prepared (i.e. Cr(III)-based MIL-100, MIL-101, and [Ru6(btc)4Cl3]), general strategies that enable reticular synthesis have not been reported. Here we describe the mechanochemical synthesis of a reticular family of crystalline Ru2[II,III]-based materials by polymerization of molecular Ru2 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 [M3L2] phases. The developed mechanochemical strategy is modular and allows for control of the primary coordination sphere of the Ru2 sites. We anticipate the strategy will provide a rational approach to incorporation of kinetically inert ions in porous crystalline coordination networks, generating a class of atomically precise mixed-metal materials.