Melt-Quenched Glasses of Metal−Organic Frameworks
Greaves, Neville G
Lampronti, Giulio I
Farha, Omar K
Hupp, Joseph T
Keen, David A
Journal of the American Chemical Society
American Chemical Society
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Bennett, T., Yue, Y., Li, P., Qiao, A., Tao, H., Greaves, N. G., Richards, T., et al. (2016). Melt-Quenched Glasses of Metal−Organic Frameworks. Journal of the American Chemical Society, 138 3484-3492. https://doi.org/10.1021/jacs.5b13220
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 3D 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 nonmetallic, organic, and metallic), and retain the basic metal−ligand connectivity of crystalline MOFs, which connects their mechanical properties to their starting chemical composition. The transfer of functionality from crystal to glass points toward new routes to tunable, functional hybrid glasses.
T.D.B. would like to thank Trinity Hall (University of Cambridge) for funding. We thank Diamond Light Source for access to beamline B18 (SP14249-1) that contributed to the results presented here. We thank Dr. Giannantonio Cibin and Dr. Stephen Parry for their assistance with the EXAFS measurements. F.B. thanks EPSRC (grant EP/M00869X/1) and the University of Liverpool for funding. O.K.F. gratefully acknowledges funding from the Army Research Office (project number W911NF-13-1-0229). S.A.T.R. is grateful for funding from the Natural Environment Research Council.
Royal Society (UF150021)
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External DOI: https://doi.org/10.1021/jacs.5b13220
This record's URL: https://www.repository.cam.ac.uk/handle/1810/253870