Pressure promoted low-temperature melting of metal–organic frameworks

Widmer, Remo N.; Lampronti, Giulio I.; Anzellini, Simone; Gaillac, Romain; Farsang, Stefan; Zhou, Chao; Belenguer, Ana M.; Wilson, Craig; Palmer, H.K.; Kleppe, Annette K.; Wharmby, Michael T.; Yu, Xia; Cohen, Seth M.; Telfer, Shane G.; Redfern, Simon A. T.; Coudert, François‐Xavier; MacLeod, Simon; Bennett, Thomas D.

doi:10.1038/s41563-019-0317-4

Cited by 170 publications

(165 citation statements)

References 66 publications

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“…S19). Both uptake amounts are significantly lower than crystalline ZIF-62, which adsorbs ~6.03 mmol/g H2 at 77 K and ~1.79 mmol/g CO2 at 273 K. 27 These results are in accordance with previous studies which demonstrate porosity in ZIF-glass materials. 28 Methane (CH4) adsorption for agZIF-62 was observed in this work at 0.21 mmol/g at 273 K (Fig.…”

Section: Resultssupporting

confidence: 91%

Guest Size Limitation in Metal-Organic Framework Crystal-Glass Composites

Ashling¹,

Macreadie²,

Southern³

et al. 2020

Preprint

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Metal-organic framework crystal-glass composites (MOF CGCs) have previously been formed by embedding crystalline MIL-53(Al) within a ZIF-62 glass (agZIF-62) matrix. Here we highlight thermal stability considerations in the formation of MOF CGCs, and subsequently report the synthesis of two novel MOF CGCs, by incorporating MIL-118, and UL-MOF-1 within agZIF-62. These new materials, alongside the prototypical MOF CGC formed using MIL-53(Al), were studied using scanning electron microscopy, powder X-ray diffraction, and gas sorption techniques. The gas uptake in composites formed from MIL-118C and UL-MOF-1 is largely dominated by the agZIF-62 matrix, suggesting that to improve the porosity of the MOF CGC, the matrix porosity must be improved, or a percolation threshold must be overcome.

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Section: Resultssupporting

confidence: 91%

Guest Size Limitation in Metal-Organic Framework Crystal-Glass Composites

Ashling¹,

Macreadie²,

Southern³

et al. 2020

Preprint

Self Cite

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“…More recently, as ystematic investigation of the phase transition of Zn-ZIF-62 was conducted using in situ PXRD and SEM at variable pressures (Figure 10 B). [51] Thee xperimentally derived pressure-temperature phase diagram of Zn-ZIF-62 shows an egative slope for the melting curve between ambient pressure and 2GPa. Theexternal pressure promotes alowering of the T m value.Inaddition, apositive slope was found at pressures higher than 2GPa.…”

Section: Methodsmentioning

confidence: 99%

A New Dimension for Coordination Polymers and Metal–Organic Frameworks: Towards Functional Glasses and Liquids

et al. 2020

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There are two categories of coordination polymers (CPs): inorganic CPs (i‐CPs) and organic ligand bridged CPs (o‐CPs). Based on the successful crystal engineering of CPs, we here propose noncrystalline states and functionalities as a new research direction for CPs. Control over the liquid or glassy states in materials is essential to obtain specific properties and functions. Several studies suggest the feasibility of obtaining liquid/glassy states in o‐CPs by design principles. The combination of metal ions and organic bridging ligands, together with the liquid/glass phase transformation, offer the possibility to transform o‐CPs into ionic liquids and other ionic soft materials. Synchrotron measurements and computational approaches contribute to elucidating the structures and dynamics of the liquid/glassy states of o‐CPs. This offers the opportunity to tune the porosity, conductivity, transparency, and other material properties. The unique energy landscape of liquid/glass o‐CPs offers opportunities for properties and functions that are complementary to those of the crystalline state.

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“…DAC experiments in MOFs have become a favourable method for exploring mechanical stability, inducing ligand‐exchange reactions, locating gas molecules in the pores, causing changes in pore size and guest content, and even inducing low‐temperature melting of amorphous frameworks . These breakthroughs have been possible due to the way in which pressure is applied to these systems inside a DAC; crystals of the MOF are placed inside the cavity and surrounded with a liquid (hydrostatic) medium in order to apply pressure evenly to the sample.…”

Section: Figurementioning

confidence: 99%

Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF

et al. 2020

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Conformational changes of linker units in metal‐organic frameworks (MOFs) are often responsible for gate‐opening phenomena in selective gas adsorption and stimuli‐responsive optical and electrical sensing behaviour. Herein, we show that pressure‐induced bathochromic shifts in both fluorescence emission and UV/Vis absorption spectra of a two‐fold interpenetrated Hf MOF, linked by 1,4‐phenylene‐bis(4‐ethynylbenzoate) ligands (Hf‐peb), are induced by rotation of the central phenyl ring of the linker, from a coplanar arrangement to a twisted, previously unseen conformer. Single‐crystal X‐ray diffraction, alongside in situ fluorescence and UV/Vis absorption spectroscopies, measured up to 2.1 GPa in a diamond anvil cell on single crystals, are in excellent agreement, correlating linker rotation with modulation of emission. Topologically isolating the 1,4‐phenylene‐bis(4‐ethynylbenzoate) units within a MOF facilitates concurrent structural and spectroscopic studies in the absence of intermolecular perturbation, allowing characterisation of the luminescence properties of a high‐energy, twisted conformation of the previously well‐studied chromophore. We expect the unique environment provided by network solids, and the capability of combining crystallographic and spectroscopic analysis, will greatly enhance understanding of luminescent molecules and lead to the development of novel sensors and adsorbents.

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Pressure promoted low-temperature melting of metal–organic frameworks

Cited by 170 publications

References 66 publications

Guest Size Limitation in Metal-Organic Framework Crystal-Glass Composites

Guest Size Limitation in Metal-Organic Framework Crystal-Glass Composites

A New Dimension for Coordination Polymers and Metal–Organic Frameworks: Towards Functional Glasses and Liquids

Correlating Pressure‐Induced Emission Modulation with Linker Rotation in a Photoluminescent MOF

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