TY - JOUR
T1 - Dynamic DMF binding in MOF-5 enables the formation of metastable cobalt-substituted MOF-5 analogues
AU - Brozek, Carl K.
AU - Michaelis, Vladimir K.
AU - Ong, Ta Chung
AU - Bellarosa, Luca
AU - López, Núria
AU - Griffin, Robert G.
AU - Dincǎ, Mircea
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/8/26
Y1 - 2015/8/26
N2 - 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.
AB - 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.
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U2 - 10.1021/acscentsci.5b00247
DO - 10.1021/acscentsci.5b00247
M3 - Article
C2 - 27162979
AN - SCOPUS:84944348801
SN - 2374-7943
VL - 1
SP - 252
EP - 260
JO - ACS Central Science
JF - ACS Central Science
IS - 5
ER -