Disorder and Sorption Preferences in a Highly Stable Fluoride- Containing Rare-Earth fcu-Type Metal−Organic Framework
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Lutton Gething, A. R. Bonity J.; Spencer, Ben F.; Whitehead, George F. S.; Vitorica-Yrezabal, Iñigo Javier; Lee, Daniel; Attfield, Martin P.Editorial
American Chemical Society
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2024-02-08Referencia bibliográfica
A. R. Bonity J. Lutton-Gething, Ben F. Spencer, George F. S. Whitehead, Iñigo J. Vitorica-Yrezabal, Daniel Lee, and Martin P. Attfield Chemistry of Materials 2024 36 (4), 1957-1965 DOI: 10.1021/acs.chemmater.3c02849
Patrocinador
EPSRC and the University of Manchester for the award of a DTG PhD studentship (EPSRC EP/R513131/1) and funding the dual source Rigaku FR-X diffractometer (EPSRC EP/P001386/1); Henry Royce Institute, funded through EPSRC grants EP/R00661X/1, EP/P025021/1, and EP/P025498/1; EPSRC and BBSRC (EP/T015063/1); University of Warwick; Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands (AWM) and the European Regional Development Fund (ERDF)Resumen
Rare-earth (RE) metal−organic frameworks (MOFs) synthesized in the
presence of fluorine-donating modulators or linkers are an important new subset of
functional MOFs. However, the exact nature of the REaXb core of the molecular building
block (MBB) of the MOF, where X is a μ2 or 3-bridging group, remains unclear.
Investigation of one of the archetypal members of this family with the stable fcu
framework topology, Y-fum-fcu-MOF (1), using a combination of experimental
techniques, including high-field (20 T) solid-state nuclear magnetic resonance
spectroscopy, has determined two sources of framework disorder involving the μ3-X
face-capping group of the MBB and the fumarate (fum) linker. The core of the MBB of 1
is shown to contain a mixture of μ3-F− and (OH)− groups with preferential occupation at the crystallographically different facecapping
sites that result in different internally lined framework tetrahedral cages. The fum linker is also found to display a disordered
arrangement involving bridging− or chelating−bridging bis-bidentate modes over the fum linker positions without influencing the
MBB orientation. This linker disorder will, upon activation, result in the creation of Y3+ ions with potentially one or two additional
uncoordinated sites possessing differing degrees of Lewis acidity. Crystallographically determined host−guest relationships for
simple sorbates demonstrate the favored sorption sites for N2, CO2, and CS2 molecules that reflect the chemical nature of both the
framework and the sorbate species with the structural partitioning of the μ3-groups apparent in determining the favored sorption site
of CS2. The two types of disorder found within 1 demonstrate the complexity of fluoride-containing RE-MOFs and highlight the
possibility to tune this and other frameworks to contain different proportions and segregations of μ3-face-capping groups and degrees
of linker disorder for specifically tailored applications.