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Instruments / Technical Area	Publication Details	Published	Actions
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
I15-Extreme Conditions I22-Small angle scattering & Diffraction	Hybrid glasses from strong and fragile metal-organic framework liquids Thomas Bennett , Jin-Chong Tan , Yuanzheng Yue , Emma Baxter , Caterina Ducati , Nicholas Terrill , Hamish Yeung , Zhongfu Zhou , Wenlin Chen , Sebastian Henke , Anthony K. Cheetham , Neville Greaves Nature Communications 6 DOI: 10.1038/ncomms9079 PMID: 26314784 Diamond Proposal Number(s): [9691, 5692] Open Access Show Abstract ▼ Abstract: Hybrid glasses connect the emerging field of metal-organic frameworks (MOFs) with the glass formation, amorphization and melting processes of these chemically versatile systems. Though inorganic zeolites collapse around the glass transition and melt at higher temperatures, the relationship between amorphization and melting has so far not been investigated. Here we show how heating MOFs of zeolitic topology first results in a low density /`perfect/' glass, similar to those formed in ice, silicon and disaccharides. This order-order transition leads to a super-strong liquid of low fragility that dynamically controls collapse, before a subsequent order-disorder transition, which creates a more fragile high-density liquid. After crystallization to a dense phase, which can be remelted, subsequent quenching results in a bulk glass, virtually identical to the high-density phase. We provide evidence that the wide-ranging melting temperatures of zeolitic MOFs are related to their network topologies and opens up the possibility of /`melt-casting/' MOF glasses.	Aug 2015

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