Quantification of Site-Specific Cation Exchange in Metal-Organic Frameworks using Multi-Wavelength Anomalous X-ray Dispersion

Carl K Brozek, Anthony Cozzolino, Simon J Test, Yu-Sheng Chen, Mircea Dinca

Research output: Contribution to journalArticle

Abstract

We employed multiwavelength anomalous X-ray dispersion to determine the relative cation occupation at two crystallographically distinct metal sites in Fe2+-, Cu2+-, and Zn2+-exchanged versions of the microporous metal–organic framework (MOF) known as MnMnBTT (BTT = 1,3,5-benzenetristetrazolate). By exploiting the dispersive differences between Mn, Fe, Cu, and Zn, the extent and location of cation exchange were determined from single crystal X-ray diffraction data sets collected near the K edges of Mn2+ and of the substituting metal, and at a wavelength remote from either edge as a reference. Comparing the anomalous dispersion between these measurements indicated that the extent of Mn2+ replacement depends on the identity of the substituting metal. We contrasted two unique methods to analyze this data with a conventional approach and evaluated their limitations with emphasis on the general application of this method to other heterometallic MOFs, where site-specific metal identification
Original languageEnglish
Pages (from-to)2998-3002
JournalChemistry of Materials
DOIs
StatePublished - Jul 2 2013

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