TY - JOUR
T1 - Disorder and Sorption Preferences in a Highly Stable Fluoride-Containing Rare-Earth fcu -Type Metal–Organic Framework
AU - Lutton-Gething, A. R. Bonity J.
AU - Spencer, Ben F.
AU - Whitehead, George F. S.
AU - Vitorica-Yrezabal, Iñigo J.
AU - Lee, Daniel
AU - Attfield, Martin P.
PY - 2024/2/27
Y1 - 2024/2/27
N2 - 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 face-capping 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.
AB - 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 face-capping 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.
KW - Crystals
KW - Diseases and disorders
KW - Ions
KW - Metal organic frameworks Molecules
KW - Molecules
U2 - 10.1021/acs.chemmater.3c02849
DO - 10.1021/acs.chemmater.3c02849
M3 - Article
SN - 0897-4756
VL - 36
SP - 1957
EP - 1965
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 4
ER -