Universität zu Köln

Christoffels, Ronja, Breitenbach (nee Stastny), Carina, Weber, Jean Patrick, Koertgen, Lisa, Tobeck, Christian, Wilhelm, Michael, Mathur, Sanjay, Neudoerfl, Joerg-Martin, Farid, Majied Sadegh Zadeh, Maslo, Melisa, Strub, Erik and Ruschewitz, Uwe . UoC-3: A Metal-Organic Framework with an Anionic Framework Based on Uranyl UO22+ Nodes and Partly Fluorinated Benzene-1,3,5-Tribenzoate Linkers. Cryst. Growth Des.. WASHINGTON: AMER CHEMICAL SOC. ISSN 1528-7505

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Abstract

The reaction of UO2(NO3) 2 center dot 6H(2)O with partly fluorinated H-3-3F-BTB (BTB3-: benzene- 1,3,5-tribenzoate) in N,N-dimethylformamide (DMF) leads to the crystallization of the metal-organic framework (MOF) [(CH3)(2)NH2][UO2(3F-BTB)]center dot xDMF, named UoC-3 (UoC: University of Cologne). X-ray singlecrystal structure analysis (Pnna, Z = 4) reveals that an anionic framework is formed, in which UO22+ nodes are connected by 3F-BTB3- ligands. Because of the fluorination of the inner ring of the linker, its three benzoate groups are tilted to an out of plane arrangement, which leads to the formation of a three-dimensional structure with large pores. This is in contrast to a known uranyl coordination polymer with the unfluorinated BTB3- linker, where an almost coplanar arrangement of the linker leads to graphene-like layers. The high porosity of UoC-3 was confirmed by N-2 gas sorption measurements, resulting in SBET = 4844 m(2)/g. The charge compensating [(CH3)(2)NH2](+) cation is formed by hydrolysis of DMF. Direct addition of [(CH3)(2)NH2]Cl to the reaction carried out in ethanol/H2O (v:v, 5:1) leads to the same MOF but with lower crystallinity. When using solvents, which hydrolyze to larger cations (e.g., N,N-diethylformamide (DEF): [(C2H5)2NH(2)](+) and N,N-di(n-butyl)formamide (DBF): [(C4H9)(2)NH2](+)), again the formation of UoC-3 was found, as confirmed by X-ray single-crystal analysis and X-ray powder diffraction. Thus, no templating effect was achieved with these cations. The exchange of the organic cations by K+ turned out to be successful, as revealed by XPS analysis. UoC-3 was also successfully tested to remove approximately 96% radioactive Cs-137(+) from aqueous solutions (93% after one regeneration cycle) while retaining its crystal structure.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Christoffels, Ronja UNSPECIFIED UNSPECIFIED UNSPECIFIED Breitenbach (nee Stastny), Carina UNSPECIFIED UNSPECIFIED UNSPECIFIED Weber, Jean Patrick UNSPECIFIED UNSPECIFIED UNSPECIFIED Koertgen, Lisa UNSPECIFIED UNSPECIFIED UNSPECIFIED Tobeck, Christian UNSPECIFIED UNSPECIFIED UNSPECIFIED Wilhelm, Michael UNSPECIFIED UNSPECIFIED UNSPECIFIED Mathur, Sanjay UNSPECIFIED UNSPECIFIED UNSPECIFIED Neudoerfl, Joerg-Martin UNSPECIFIED UNSPECIFIED UNSPECIFIED Farid, Majied Sadegh Zadeh UNSPECIFIED UNSPECIFIED UNSPECIFIED Maslo, Melisa UNSPECIFIED UNSPECIFIED UNSPECIFIED Strub, Erik UNSPECIFIED UNSPECIFIED UNSPECIFIED Ruschewitz, Uwe UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-577753
DOI:	10.1021/acs.cgd.1c01199
Journal or Publication Title:	Cryst. Growth Des.
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1528-7505
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language LANTHANIDE COORDINATION POLYMERS; CRYSTAL-STRUCTURES; REMOVAL; URANIUM; XPS; TETRAFLUOROTEREPHTHALATE; CESIUM; SPECTROSCOPY; HYDROLYSIS; COMPLEXES Multiple languages Chemistry, Multidisciplinary; Crystallography; Materials Science, Multidisciplinary Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/57775