Journal
INORGANIC CHEMISTRY
Volume 52, Issue 7, Pages 4011-4016Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic400048g
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Funding
- Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering [DE-FG02-08ER46519]
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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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