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Site-specific metal and ligand substitutions in a microporous Mn2+-based metal–organic framework.
- Source :
- Dalton Transactions: An International Journal of Inorganic Chemistry; 3/14/2016, Vol. 45 Issue 10, p4431-4438, 8p
- Publication Year :
- 2016
-
Abstract
- The precise tuning of the structural and chemical features of microporous metal–organic frameworks (MOFs) is a crucial endeavour for developing materials with properties that are suitable for specific applications. In recent times, techniques for preparing frameworks consisting of mixed-metal or ligand compositions have emerged. However, controlled spatial organisation of the components within these structures at the molecular scale is a difficult challenge, particularly when species possessing similar geometries or chemical properties are used. Here, we describe the synthesis of mixed-metal and ligand variants possessing the Mn<subscript>3</subscript>L<subscript>3</subscript> (Mn-MOF-1; H<subscript>2</subscript>L = bis(4-(4′-carboxyphenyl)-3,5-dimethylpyrazolyl)methane) structure type. In the case of mixed-ligand synthesis using a mixture of L and its trifluoromethyl-functionalised derivative (H<subscript>2</subscript>L′ = bis(4-(4′-carboxyphenyl)-3,5-di(trifluoromethyl)pyrazolyl)methane), a mixed-ligand product in which the L′ species predominanantly occupies the pillar sites lining the pores is obtained. Meanwhile, post-synthetic metal exchange of the parent Mn<subscript>3</subscript>L<subscript>3</subscript> compound using Fe<superscript>2+</superscript> or Fe<superscript>3+</superscript> ions results in a degree of cation exchange at the trinuclear carboxylate-based clusters and metalation at the pillar bispyrazolate sites. The results demonstrate the versatility of the Mn<subscript>3</subscript>L<subscript>3</subscript> structure type toward both metal and ligand substitutions, and the potential utility of site-specific functionalisations in achieving even greater precision in the tuning of MOFs. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 14779226
- Volume :
- 45
- Issue :
- 10
- Database :
- Complementary Index
- Journal :
- Dalton Transactions: An International Journal of Inorganic Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 113447545
- Full Text :
- https://doi.org/10.1039/c5dt05023e