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Instruments / Technical Area	Publication Details	Published	Actions
I15-Extreme Conditions	Survival of zirconium-based metal–organic framework crystallinity at extreme pressures Georgina P. Robertson , Sara Mosca , Celia Castillo-Blas , Florencia A. Son , Omar K. Farha , David A. Keen , Simone Anzellini , Thomas D. Bennett Inorganic Chemistry 28 DOI: 10.1021/acs.inorgchem.2c04428 Diamond Proposal Number(s): [31314] Open Access Show Abstract ▼ Abstract: Recent research on metal–organic frameworks (MOFs) has shown a shift from considering only the crystalline high-porosity phases to exploring their amorphous counterparts. Applying pressure to a crystalline MOF is a common method of amorphization, as MOFs contain large void spaces that can collapse, reducing the accessible surface area. This can be either a desired change or indeed an unwanted side effect of the application of pressure. In either case, understanding the MOF’s pressure response is extremely important. Three such MOFs with varying pore sizes (UiO-66, MOF-808, and NU-1000) were investigated using in situ high-pressure X-ray diffraction and Raman spectroscopy. Partial crystallinity was observed in all three MOFs above 10 GPa, along with some recovery of crystallinity on return to ambient conditions if the frameworks were not compressed above thresholds of 13.3, 14.2, and 12.3 GPa for UiO-66, MOF-808, and NU-1000, respectively. This threshold was marked by an unexpected increase in one or more lattice parameters with pressure in all MOFs. Comparison of compressibility between MOFs suggests penetration of the pressure-transmitting oil into MOF-808 and NU-1000. The survival of some crystallinity above 10 GPa in all of these MOFs despite their differing pore sizes and extents of oil penetration demonstrates the importance of high-pressure characterization of known structures.	Jun 2023
B18-Core EXAFS	Melt-quenched glasses of metal–organic frameworks Thomas Bennett , Yuanzheng Yue , Peng Li , Ang Qiao , Haizheng Tao , Neville Greaves , Tom Richards , Giulio Lampronti , Simon Redfern , Frédéric Blanc , Omar K. Farha , Joseph T. Hupp , Anthony K. Cheetham , David Keen Journal Of The American Chemical Society DOI: 10.1021/jacs.5b13220 Diamond Proposal Number(s): [14249] Open Access Show Abstract ▼ Abstract: Crystalline solids dominate the field of metal-organic frameworks (MOFs), with access to the liquid and glass states of matter usually prohibited by relatively low temperatures of thermal decomposition. In this work, we give due consideration to framework chemistry and topology to expand the phenomenon of the melting of three-dimensional MOFs, linking crystal chemistry to framework melting temperature and kinetic fragility of the glass-forming liquids. Here we show that melting temperatures can be lowered by altering the chemistry of the crystalline MOF state, which provides a route to facilitate the melting of other MOFs. The glasses formed upon vitrification are chemically and structurally distinct from the three other existing categories of melt-quenched glasses (inorganic non-metallic, organic and metallic), and retain the basic metal-ligand connectivity of crystalline MOFs, which connects their mechanical properties to starting chemical composition. The transfer of functionality from crystal to glass points towards new routes to tunable, functional hybrid glasses.	Feb 2016

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