Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2020 Mar 27;367(6485):1473-1476.
doi: 10.1126/science.aaz0251.

Ultrahigh-field 67Zn NMR reveals short-range disorder in zeolitic imidazolate framework glasses

Rasmus S K Madsen #  1 , Ang Qiao #  1 , Jishnu Sen  2 , Ivan Hung  3 , Kuizhi Chen  3 , Zhehong Gan  3 , Sabyasachi Sen  4 , Yuanzheng Yue  5   6   7
Affiliations

Ultrahigh-field 67Zn NMR reveals short-range disorder in zeolitic imidazolate framework glasses

Rasmus S K Madsen et al. Science. .

Abstract

The structure of melt-quenched zeolitic imidazole framework (ZIF) glasses can provide insights into their glass-formation mechanism. We directly detected short-range disorder in ZIF glasses using ultrahigh-field zinc-67 solid-state nuclear magnetic resonance spectroscopy. Two distinct Zn sites characteristic of the parent crystals transformed upon melting into a single tetrahedral site with a broad distribution of structural parameters. Moreover, the ligand chemistry in ZIFs appeared to have no controlling effect on the short-range disorder, although the former affected their phase-transition behavior. These findings reveal structure-property relations and could help design metal-organic framework glasses.

PubMed Disclaimer

Conflict of interest statement

Competing interests: The authors declare that they have no competing interests.

Figures

Fig. 1.
Fig. 1.. Phase transitions, glass formation and glass transition for ZIFs.
(A) First and second DSC upscans for both ZIF-4 and ZIF-62, respectively. (B) XRD patterns of as-prepared ZIF-4 crystals, ZIF-zni crystals, ZIF-4 glass, ZIF-62 crystals and ZIF-62 glass. (C) Conceptual schematic representation of the structural change from crystalline ZIF (see powder sample) to its glassy state (see transparent bulk sample) during melt-quenching.
Fig. 2.
Fig. 2.. Short-range order of crystalline ZIFs.
Experimental (solid black line) and simulated (dashed red line) 67Zn MAS NMR spectra of crystalline ZIF-4 (A, B), ZIF-62 (C, D), and ZIF-zni (E, F) collected at 19.5 and 35.2 T. Individual simulation components (dot-dashed blue lines) are vertically offset for clarity.
Fig. 3.
Fig. 3.. Comparison of short-range structure between ZIF glasses and crystals.
Experimental (solid black line) and simulated (dashed red line) 67Zn MAS NMR spectra for ZIF-4 glass (A, B) and the standard ZIF-62 glass (C, D) at different magnetic fields. Direct comparison of 67Zn MAS NMR spectra collected at 35.2 T between ZIF-4 crystal, ZIF-zni crystal, ZIF-4 glass (E), as well as spectra of ZIF-62 crystal and glass (F).
See this image and copyright information in PMC

References

    1. Angell CA, Formation of glasses from liquids and biopolymers. Science 267, 1924–1935 (1995). - PubMed
    1. Greaves GN, Sen S, Inorganic glasses, glass-forming liquids and amorphizing solids. Adv. Phys. 56, 1–166 (2007).
    1. Bennett TD, Tan J-C, Yue YZ, Baxter E, Ducati C, Terrill NJ, Yeung HH-M, Zhou Z, Chen W, Henke S, Hybrid glasses from strong and fragile metal-organic framework liquids. Nat. Commun. 6, 8079 (2015). - PMC - PubMed
    1. Umeyama D, Funnell NP, Cliffe MJ, Hill JA, Goodwin AL, Hijikata Y, Itakura T, Okubo T, Horike S, Kitagawa S, Glass formation via structural fragmentation of a 2D coordination network. Chem. Commun. 51, 12728–12731 (2015). - PubMed
    1. Bennett TD, Yue YZ, Li P, Qiao A, Tao H, Greaves NG, Richards T, Lampronti GI, Redfern SAT, Blanc F, Farha OK, Hupp JT, Cheetham AK, Keen DA, Melt-quenched glasses of metal-organic frameworks. J. Am. Chem. Soc. 138, 3484–3492 (2016). - PubMed

Publication types