Molecular promoting of aluminum metal-organic framework topology MIL-101 by N, N-dimethylformamide

Maarten G. Goesten; Pieter C.M.M. Magusin; Evgeny A. Pidko; Brahim Mezari; Emiel J.M. Hensen; Freek Kapteijn; Jorge Gascon

doi:10.1021/ic402198a

Molecular promoting of aluminum metal-organic framework topology MIL-101 by N, N-dimethylformamide

Maarten G. Goesten^*, Pieter C.M.M. Magusin, Evgeny A. Pidko, Brahim Mezari, Emiel J.M. Hensen, Freek Kapteijn, Jorge Gascon

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

47 Scopus citations

Abstract

In situ NMR and DFT modeling demonstrate that N,N-dimethylformamide (DMF) promotes the formation of metal-organic framework NH₂-MIL-101(Al). In situ NMR studies show that upon dissociation of an aluminum-coordinated aqua ligand in NH₂-MOF-235(Al), DMF forms a H-Cl-DMF complex during synthesis. This reaction induces a transformation from the MOF-235 topology into the MIL-101 topology. Electronic structure density functional theory (DFT) calculations show that the use of DMF instead of water as the synthesis solvent decreases the energy gap between the kinetically favored MIL-101 and thermodynamically favored MIL-53 products. DMF therefore promotes MIL-101 topology both kinetically and thermodynamically.

Original language	English (US)
Pages (from-to)	882-887
Number of pages	6
Journal	Inorganic chemistry
Volume	53
Issue number	2
DOIs	https://doi.org/10.1021/ic402198a
State	Published - Jan 21 2014
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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title = "Molecular promoting of aluminum metal-organic framework topology MIL-101 by N, N-dimethylformamide",

abstract = "In situ NMR and DFT modeling demonstrate that N,N-dimethylformamide (DMF) promotes the formation of metal-organic framework NH2-MIL-101(Al). In situ NMR studies show that upon dissociation of an aluminum-coordinated aqua ligand in NH2-MOF-235(Al), DMF forms a H-Cl-DMF complex during synthesis. This reaction induces a transformation from the MOF-235 topology into the MIL-101 topology. Electronic structure density functional theory (DFT) calculations show that the use of DMF instead of water as the synthesis solvent decreases the energy gap between the kinetically favored MIL-101 and thermodynamically favored MIL-53 products. DMF therefore promotes MIL-101 topology both kinetically and thermodynamically.",

author = "Goesten, {Maarten G.} and Magusin, {Pieter C.M.M.} and Pidko, {Evgeny A.} and Brahim Mezari and Hensen, {Emiel J.M.} and Freek Kapteijn and Jorge Gascon",

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doi = "10.1021/ic402198a",

language = "English (US)",

volume = "53",

pages = "882--887",

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TY - JOUR

T1 - Molecular promoting of aluminum metal-organic framework topology MIL-101 by N, N-dimethylformamide

AU - Goesten, Maarten G.

AU - Magusin, Pieter C.M.M.

AU - Pidko, Evgeny A.

AU - Mezari, Brahim

AU - Hensen, Emiel J.M.

AU - Kapteijn, Freek

AU - Gascon, Jorge

PY - 2014/1/21

Y1 - 2014/1/21

N2 - In situ NMR and DFT modeling demonstrate that N,N-dimethylformamide (DMF) promotes the formation of metal-organic framework NH2-MIL-101(Al). In situ NMR studies show that upon dissociation of an aluminum-coordinated aqua ligand in NH2-MOF-235(Al), DMF forms a H-Cl-DMF complex during synthesis. This reaction induces a transformation from the MOF-235 topology into the MIL-101 topology. Electronic structure density functional theory (DFT) calculations show that the use of DMF instead of water as the synthesis solvent decreases the energy gap between the kinetically favored MIL-101 and thermodynamically favored MIL-53 products. DMF therefore promotes MIL-101 topology both kinetically and thermodynamically.

AB - In situ NMR and DFT modeling demonstrate that N,N-dimethylformamide (DMF) promotes the formation of metal-organic framework NH2-MIL-101(Al). In situ NMR studies show that upon dissociation of an aluminum-coordinated aqua ligand in NH2-MOF-235(Al), DMF forms a H-Cl-DMF complex during synthesis. This reaction induces a transformation from the MOF-235 topology into the MIL-101 topology. Electronic structure density functional theory (DFT) calculations show that the use of DMF instead of water as the synthesis solvent decreases the energy gap between the kinetically favored MIL-101 and thermodynamically favored MIL-53 products. DMF therefore promotes MIL-101 topology both kinetically and thermodynamically.

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U2 - 10.1021/ic402198a

DO - 10.1021/ic402198a

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JO - Inorganic chemistry

JF - Inorganic chemistry

IS - 2

ER -

Molecular promoting of aluminum metal-organic framework topology MIL-101 by N, N-dimethylformamide

Abstract

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