Disorder and Sorption Preferences in a Highly Stable Fluoride-Containing Rare-Earth fcu-Type Metal-Organic Framework.

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.

Bimetallic Aluminum- and Niobium-Doped MCM-41 for Efficient Conversion of Biomass-Derived 2-Methyltetrahydrofuran to Pentadienes.

The production of conjugated C4-C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)-atomically doped mesoporous silica, denoted as AlNb-MCM-41, which affords quantitative conversion of 2-methyltetrahydrofuran (2-MTHF) to pentadienes with a high selectivity of 91 %. The incorporation of AlIII and NbV sites into the framework of AlNb-MCM-41 has effectively tuned the nature and distribution of Lewis and Brønsted acid sites within the structure. Operando X-ray absorption, diffuse reflectance infrared and solid-state NMR spectroscopy collectively reveal the molecular mechanism of the conversion of adsorbed 2-MTHF over AlNb-MCM-41. Specifically, the atomically-dispersed NbV sites play an important role in binding 2-MTHF to drive the conversion. Overall, this study highlights the potential of hetero-atomic mesoporous solids for the manufacture of renewable materials.