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

We employed multiwavelength anomalous X-ray dispersion to determine the relative cation occupation at two crystallographically distinct metal sites in Fe 2+-, Cu 2+-, and Zn 2+-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 Mn 2+ 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 Mn 2+ 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 is fundamental to tuning catalytic and physical properties.
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  1. MIT
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Publication Date:
OSTI Identifier:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 25; Journal Issue: (15) ; 08, 2013
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org:
Country of Publication:
United States