title: Dynamic DMF Binding in MOF-5 Enables the Formation of Metastable Cobalt-Substituted MOF-5 Analogues.
abstract: Multinuclear solid-state nuclear magnetic resonance, mass spectrometry, first-principles molecular dynamics simulations, and other complementary evidence reveal that the coordination environment around the Zn(2+) ions in MOF-5, one of the most iconic materials among metal-organic frameworks (MOFs), is not rigid. The Zn(2+) 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-x Co x O(terephthalate)3 (x > 1) materials, which have not been accessible through typical high-temperature solvothermal routes thus far.
authors.affiliation: Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Carl K
authors.initials: CK
authors.lastname: Brozek
authors.affiliation: Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States; Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Vladimir K
authors.initials: VK
authors.lastname: Michaelis
authors.affiliation: Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States; Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Ta-Chung
authors.initials: TC
authors.lastname: Ong
authors.affiliation: Institute of Chemical Research of Catalonia, ICIQ , Avinguda dels Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Luca
authors.initials: L
authors.lastname: Bellarosa
authors.affiliation: Institute of Chemical Research of Catalonia, ICIQ , Avinguda dels Països Catalans 16, 43007, Tarragona, Spain.
authors.forename: Núria
authors.initials: N
authors.lastname: López
authors.affiliation: Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States; Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Robert G
authors.initials: RG
authors.lastname: Griffin
authors.affiliation: Department of Chemistry and Francis Bitter Magnet Laboratory, Massachusetts Institute of Technology , 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
authors.forename: Mircea
authors.initials: M
authors.lastname: Dincă