Glassy behaviour of mechanically amorphised ZIF-62 isomorphs

Thorne, Michael F.; Sapnik, Adam; McHugh, Lauren; Bumstead, Alice; Castillo‐Blas, Celia; Keeble, Dean S.; Lopez, Maria Diaz; Chater, Philip A.; Keen, David A.; Bennett, Thomas D.

doi:10.1039/d1cc03469c

Cited by 24 publications

(21 citation statements)

References 29 publications

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“…Extended milling of ZIF-62 isomorphs (Figure ) Zn(Im) 2– x (bIm) x ( x = 0.3, 0.5, 1.0) during mechano-synthesis results in MIGs, with T g ranging between 318 and 411 °C . The observed values are lower than those of their MQG counterparts.…”

Section: Mechanically Induced Glassesmentioning

confidence: 99%

“…Extended milling of ZIF-62 isomorphs (Figure 10) Zn-(Im) 2−x (bIm) x (x = 0.3, 0.5, 1.0) during mechano-synthesis results in MIGs, with T g ranging between 318 and 411 °C. 171 The observed values are lower than those of their MQG counterparts. The difference in thermal behavior is hypothesized to be the result of the differences in particle size.…”

Section: Zeolitic Imidazolate Frameworkmentioning

confidence: 99%

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Metal–Organic Network-Forming Glasses

2022

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The crystal−liquid−glass phase transition of coordination polymers (CPs) and metal−organic frameworks (MOFs) offers attractive opportunities as a new class of amorphous materials. Unlike conventional glasses, coordination chemistry allows the utilization of rational design concepts to fine-tune the desired properties. Although the glassy state has been rare in CPs/MOFs, it exhibits diverse advantages complementary to their crystalline counterparts, including improved mass transport, optical properties, mechanical properties, and the ability to form grain-boundary-free monoliths. This Review discusses the current achievements in improving the understanding of anomalous phase transitions in CPs/MOFs. We elaborate on the criteria for classifying CP/MOF glasses and comprehensively discuss the three common strategies employed to obtain a glassy state. We include all CP/MOF glass research progress since its inception, discuss the current challenges, and express our perspective on future research directions. CONTENTS 7.5. Thermal Conductivity 4194 8. Outlook and Conclusion 4194 8.1. Crystal Melting and Glass Formation 4195 8.2. Alternative Routes to Obtain a Glassy State 4195 8.3. Structural Identification 4196 8.4. Application 4196 Associated Content 4196 Special Issue Paper 4196 Author Information 4196 Corresponding Author 4196 Author 4197 Notes 4197 Biographies 4197 Acknowledgments 4197 Abbreviations 4197 References 4198

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Section: Mechanically Induced Glassesmentioning

confidence: 99%

Section: Zeolitic Imidazolate Frameworkmentioning

confidence: 99%

Metal–Organic Network-Forming Glasses

2022

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“…Interestingly, the largest feature in this region of the distortion was at 5 Å which is not commonly a peak position that is described for the Zn–Im–Zn motif 64 . Closer inspection of the partial PDFs reveal that Zn–C and N–C contribute to this region of the PDF, possibly suggesting that these interactions are particularly important during the melting process 66 . Importantly, visual inspection of the PDFs themselves only display a slight reduction in intensity of a shoulder peak at 5 Å which could easily be overlooked; through analysing the distortion component, we uncover the importance of this region during melting.…”

Section: Resultsmentioning

confidence: 99%

Multivariate analysis of disorder in metal–organic frameworks

et al. 2022

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The rational design of disordered frameworks is an appealing route to target functional materials. However, intentional realisation of such materials relies on our ability to readily characterise and quantify structural disorder. Here, we use multivariate analysis of pair distribution functions to fingerprint and quantify the disorder within a series of compositionally identical metal–organic frameworks, possessing different crystalline, disordered, and amorphous structures. We find this approach can provide powerful insight into the kinetics and mechanism of structural collapse that links these materials. Our methodology is also extended to a very different system, namely the melting of a zeolitic imidazolate framework, to demonstrate the potential generality of this approach across many areas of disordered structural chemistry.

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“…A further peak is also present around 5 Å in the ePDF data, which has been seen in other XPDF work. 67 We attribute the notable intensity differences around 5 and 6 Å are a result of the relative differences in X-ray and electron scattering, with relatively stronger scattering of the associated Zn-H peaks around 5 Å (ref. 66) and relatively weaker Zn-Zn scattering around 6 Å expected in the electron PDF.…”

Section: Electron and X-ray Pdf Comparisonmentioning

confidence: 99%