Tandem Postsynthetic Metal Ion and Ligand Exchange in Zeolitic Imidazolate Frameworks

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• 作者：Honghan Fei ; John F. Cahill ; Kimberly A. Prather ; Seth M. Cohen
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：April 1, 2013
• 年：2013
• 卷：52
• 期：7
• 页码：4011-4016
• 全文大小：349K
• 年卷期：v.52,no.7(April 1, 2013)
• ISSN：1520-510X

文摘

Herein, we report a general postsynthetic exchange (PSE) approach to introduce a redox-active transition metal, specifically Mn(II), into 鈥渋nert鈥?zeolitic imidazolate frameworks (ZIFs), a subclass of metal鈥搊rganic 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鈥揈mmett鈥揟eller (BET) surface area analysis. In addition, stepwise 鈥渢andem鈥?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.