Dynamic DMF Binding in MOF-5 Enables the Formation of Metastable Cobalt-Substituted MOF-5 Analogues

• Main Authors: Bellarosa, Luca (Author), López, Núria (Author), Brozek, Carl Kavanaugh (Contributor), Michaelis, Vladimir K. (Contributor), Ong, Ta-Chung (Contributor), Griffin, Robert Guy (Contributor), Dinca, Mircea (Contributor)
• Other Authors: Massachusetts Institute of Technology. Department of Chemistry (Contributor), Francis Bitter Magnet Laboratory (Massachusetts Institute of Technology) (Contributor)
• Format: Article
• Language: English
• Published: American Chemical Society (ACS), 2016-11-01T16:05:40Z.
• Subjects: Article
• Online Access: Get fulltext

Multinuclear solid-state nuclear magnetic resonance, mass spectrometry, first-principles molecular dynamics simulations, and other complementary evidence reveal that the coordination environment around the Zn2+ ions in MOF-5, one of the most iconic materials among metal-organic frameworks (MOFs), is not rigid. The Zn2+ ions bind solvent molecules, thereby increasing their coordination number, and dynamically dissociate from the framework itself. On average, one ion in each cluster has at least one coordinated N,N-dimethylformamide (DMF) molecule, such that the formula of as-synthesized MOF-5 is defined as Zn4O(BDC)3(DMF)x (x = 1-2). Understanding the dynamic behavior of MOF-5 leads to a rational low-temperature cation exchange approach for the synthesis of metastable Zn4-xCoxO(terephthalate)3 (x > 1) materials, which have not been accessible through typical high-temperature solvothermal routes thus far.
National Science Foundation (U.S.) (NSF CAREER Award (DMR-1452612))
National Science Foundation (U.S.) (NSF Graduate Research Fellowship Grant 1122374)
National Institutes of Health (U.S.) (grant EB002026)
Natural Sciences and Engineering Research Council of Canada
Government of Canada (Banting postdoctoral fellowship)