Journal
SCIENCE ADVANCES
Volume 4, Issue 3, Pages -Publisher
AMER ASSOC ADVANCEMENT SCIENCE
DOI: 10.1126/sciadv.aao6827
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Funding
- National Natural Science Foundation of China [51772223]
- 1000 Talents Program of China
- Strategy Scientists Program of Wuhan University of Technology
- Corning Incorporated
- Royal Society
- Slovenian Research Agency
- Australian Research Council [DE140101359]
- Veski Inspiring Women Fellowship
- Julius Career Award from the Commonwealth Scientific and Industrial Research Organization
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Glass-forming ability (GFA) is the ability of a liquid to avoid crystallization during cooling. Metal-organic frameworks (MOFs) are a new class of glass formers (1-3), with hitherto unknown dynamic and thermodynamic properties. We report the discovery of a new series of tetrahedral glass systems, zeolitic imidazolate framework-62 (ZIF-62) [Zn(Im(2-x)bIm(x))], which have ultrahigh GFA, superior to any other known glass formers. This ultrahigh GFA is evidenced by a high viscosity eta (10(5) Pa.s) at the melting temperature T-m, a large crystal-glass network density deficit (Delta rho/rho(g))(network), no crystallization in supercooled region on laboratory time scales, a low fragility (m = 23), an extremely high Poisson's ratio (nu = 0.45), and the highest T-g/T-m ratio (0.84) ever reported. T-m and T-g both increase with benzimidazolate (bIm) content but retain the same ultrahigh T-g/T-m ratio, owing to high steric hindrance and frustrated network dynamics and also to the unusually low enthalpy and entropy typical of the soft and flexible nature of MOFs. On the basis of these versatile properties, we explain the exceptional GFA of the ZIF-62 system.
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