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Postsynthetic Ligand and Ion Exchange in Robust Metal-Organic Frameworks.
MedLine Citation:
PMID:  23039827     Owner:  NLM     Status:  Publisher    
Postsynthetic ligand and metal ion exchange (PSE) processes are shown to readily occur in several 'inert' metal-organic frameworks (MOFs), including zeolitic imidazolate frameworks (ZIFs). Ligand exchange can occur between solid samples, as was demonstrated under relatively mild conditions with two robust, topologically distinct MOFs, MIL-53(Al) and MIL-68(In) (MIL = Materials of the Institut Lavoisier). Interestingly, ligand PSE is not observed with MIL-101(Cr), which is attributed to the kinetic inertness of the Cr(III) ion. In addition to ligand exchange, metal ion (cation) PSE was also studied between intact MOF microcrystalline particle. Metal ion transfer between MIL-53(Al) and MIL-53(Fe) was readily observed. These PSE reactions were monitored and the products characterized by a number of techniques, including aerosol time-of-flight mass spectrometry (ATOFMS), which permits single-particle compositional analysis. To show the potential synthetic utility of this approach, the PSE process was used to prepare the first Ti(IV) analogue of the robust UiO-66(Zr) (UiO-66 = University of Oslo) framework. Finally, experiments to rule out mechanisms other than PSE (i.e., aggregation, dissolution/recrystallization) were performed. The results demonstrate that PSE, of either ligands or cations, is common even with highly robust MOFs such as UiO-66(Zr), MILs, and ZIFs. Furthermore, it is shown that PSE is useful in preparing novel materials that cannot be obtained via other synthetic methods.
Min Kim; John F Cahill; Honghan Fei; Kimberly Ann Prather; Seth M Cohen
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Publication Detail:
Type:  JOURNAL ARTICLE     Date:  2012-10-8
Journal Detail:
Title:  Journal of the American Chemical Society     Volume:  -     ISSN:  1520-5126     ISO Abbreviation:  J. Am. Chem. Soc.     Publication Date:  2012 Oct 
Date Detail:
Created Date:  2012-10-8     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  7503056     Medline TA:  J Am Chem Soc     Country:  -    
Other Details:
Languages:  ENG     Pagination:  -     Citation Subset:  -    
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