Tandem Postsynthetic Metal Ion and Ligand Exchange in Zeolitic Imidazolate Frameworks

TitleTandem Postsynthetic Metal Ion and Ligand Exchange in Zeolitic Imidazolate Frameworks
Publication TypeJournal Article
Year of Publication2013
AuthorsFei HH, Cahill JF, Prather KA, Cohen SM
JournalInorganic Chemistry
Volume52
Pagination4011-4016
Date Published2013/04
Type of ArticleArticle
ISBN Number0020-1669
Accession NumberWOS:000317094300067
Keywordsadsorption; crystal; design; functionalization; linkers; mofs; organic frameworks; stability; water
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.

DOI10.1021/ic400048g
Short TitleInorg. Chem.
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