Tandem postsynthetic metal ion and ligand exchange in zeolitic imidazolate frameworks

Honghan Fei; John F. Cahill; Kimberly A. Prather; Seth M. Cohen

doi:10.1021/ic400048g

Tandem postsynthetic metal ion and ligand exchange in zeolitic imidazolate frameworks

Honghan Fei, John F. Cahill, Kimberly A. Prather, Seth M. Cohen

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211 Scopus citations

Abstract

Herein, we report a general postsynthetic exchange (PSE) approach to introduce a redox-active transition metal, specifically Mn(II), into "inert" zeolitic imidazolate frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs). It is shown that metal ion PSE occurs in ZIF-71 (RHO topology) and ZIF-8 (SOD topology) under ambient conditions. The metal exchanged ZIFs are the first porous, Mn(II)-based ZIFs and a rare example of ZIFs with two transition metal centers in a single lattice. Exchanged materials are characterized by scanning electron microscopy-energy dispersed X-ray spectroscopy (SEM-EDX), aerosol time-of-flight mass spectrometry (ATOFMS), X-ray fluorescence spectroscopy (XRF), and Brunauer-Emmett-Teller (BET) surface area analysis. In addition, stepwise "tandem" PSE strategies are described to exchange of metal ions and organic linkers consecutively in ZIFs. These findings are important for probing the chemical dynamics of ZIFs, despite their high crystallinity and robustness, and inspire the more widespread use of PSE to prepare multimetallic and multifunctional MOFs.

Original language	English
Pages (from-to)	4011-4016
Number of pages	6
Journal	Inorganic Chemistry
Volume	52
Issue number	7
DOIs	https://doi.org/10.1021/ic400048g
State	Published - Apr 1 2013
Externally published	Yes

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title = "Tandem postsynthetic metal ion and ligand exchange in zeolitic imidazolate frameworks",

abstract = "Herein, we report a general postsynthetic exchange (PSE) approach to introduce a redox-active transition metal, specifically Mn(II), into {"}inert{"} zeolitic imidazolate frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs). It is shown that metal ion PSE occurs in ZIF-71 (RHO topology) and ZIF-8 (SOD topology) under ambient conditions. The metal exchanged ZIFs are the first porous, Mn(II)-based ZIFs and a rare example of ZIFs with two transition metal centers in a single lattice. Exchanged materials are characterized by scanning electron microscopy-energy dispersed X-ray spectroscopy (SEM-EDX), aerosol time-of-flight mass spectrometry (ATOFMS), X-ray fluorescence spectroscopy (XRF), and Brunauer-Emmett-Teller (BET) surface area analysis. In addition, stepwise {"}tandem{"} PSE strategies are described to exchange of metal ions and organic linkers consecutively in ZIFs. These findings are important for probing the chemical dynamics of ZIFs, despite their high crystallinity and robustness, and inspire the more widespread use of PSE to prepare multimetallic and multifunctional MOFs.",

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AU - Fei, Honghan

AU - Cahill, John F.

AU - Prather, Kimberly A.

AU - Cohen, Seth M.

PY - 2013/4/1

Y1 - 2013/4/1

N2 - Herein, we report a general postsynthetic exchange (PSE) approach to introduce a redox-active transition metal, specifically Mn(II), into "inert" zeolitic imidazolate frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs). It is shown that metal ion PSE occurs in ZIF-71 (RHO topology) and ZIF-8 (SOD topology) under ambient conditions. The metal exchanged ZIFs are the first porous, Mn(II)-based ZIFs and a rare example of ZIFs with two transition metal centers in a single lattice. Exchanged materials are characterized by scanning electron microscopy-energy dispersed X-ray spectroscopy (SEM-EDX), aerosol time-of-flight mass spectrometry (ATOFMS), X-ray fluorescence spectroscopy (XRF), and Brunauer-Emmett-Teller (BET) surface area analysis. In addition, stepwise "tandem" PSE strategies are described to exchange of metal ions and organic linkers consecutively in ZIFs. These findings are important for probing the chemical dynamics of ZIFs, despite their high crystallinity and robustness, and inspire the more widespread use of PSE to prepare multimetallic and multifunctional MOFs.

AB - Herein, we report a general postsynthetic exchange (PSE) approach to introduce a redox-active transition metal, specifically Mn(II), into "inert" zeolitic imidazolate frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs). It is shown that metal ion PSE occurs in ZIF-71 (RHO topology) and ZIF-8 (SOD topology) under ambient conditions. The metal exchanged ZIFs are the first porous, Mn(II)-based ZIFs and a rare example of ZIFs with two transition metal centers in a single lattice. Exchanged materials are characterized by scanning electron microscopy-energy dispersed X-ray spectroscopy (SEM-EDX), aerosol time-of-flight mass spectrometry (ATOFMS), X-ray fluorescence spectroscopy (XRF), and Brunauer-Emmett-Teller (BET) surface area analysis. In addition, stepwise "tandem" PSE strategies are described to exchange of metal ions and organic linkers consecutively in ZIFs. These findings are important for probing the chemical dynamics of ZIFs, despite their high crystallinity and robustness, and inspire the more widespread use of PSE to prepare multimetallic and multifunctional MOFs.

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Tandem postsynthetic metal ion and ligand exchange in zeolitic imidazolate frameworks

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