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 m...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2020-06, Vol.59 (27), p.10878-10883
Main Authors: Gao, Wen‐Yang, Sur, Aishanee, Wang, Chen‐Hao, Lorzing, Gregory R., Antonio, Alexandra M., Taggart, Garrett A., Ezazi, Andrew A., Bhuvanesh, Nattamai, Bloch, Eric D., Powers, David C.
Format: Article
Language:English
Subjects:
Carboxylic acids
Coordination polymers
Copper
Crystal structure
crystalline materials
Crystallinity
kinetically inert metals
mechanochemistry
Metal ions
Metal-organic frameworks
Metals
Polymers
primary coordination sphere
reticular chemistry
Solid solutions
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Summary: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 [M3L2] 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. Reticular mechanopolymerization of labile metal nodes and kinetically inert metallomonomers provides a rational synthetic approach to controlling the primary coordination sphere of inert metal nodes and the distribution of metal sites with atomistic precision.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202002638