A metal-organic framework with ultrahigh glass-forming ability

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- bIm )], which have ultrahigh GFA, superior to any other known glass formers. This ultrahigh GFA is evidenced by a high viscosity η (10⁵ Pa·s) at the melting temperature T_m, a large crystal-glass network density deficit (Δρ/ρ_g)_network, no crystallization in supercooled region on laboratory time scales, a low fragility (m = 23), an extremely high Poisson's ratio (ν = 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.