Zinc Halide Flux-Assisted Vitrification of Metal–Organic Frameworks Enables Chemical Diversification and Tunable Gas Sorption

The vitrification of metal–organic frameworks (MOFs) enables melt processing into bulk, shaped and membrane-type porous materials, yet the limited chemical diversity of existing MOF glass formers rest...

doi.org

Alkali-ion-modified zeolitic imidazolate framework glasses - Nature Chemistry

The properties of metal–organic framework glasses can be modulated by additives, but understanding how they modify the glass network is challenging. Now, alkali-modifier sites in MOF glasses have been...

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Understanding the High-Pressure Behavior of Honeycomb-Like Metal–Organic Frameworks with Open Metal Sites: Influence of Metal Identity, Linker Extension and Diamine Functionalization

MOF-74 (M2(dobdc); dobdc4– = 2,5-dioxido-1,4-benzenedicarboxylate) and its isoreticular derivatives represent a chemically versatile class of metal–organic frameworks (MOFs) with high densities of ope...

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Luminescent Chiral Molecular Glasses by Melt‐Quenching Enantiopure BINAP

Melt-quenching of enantiopure BINAP yields transparent chiral molecular glasses that retain axial chirality and display blue-shifted luminescence together with strongly enhanced circularly polarized ...

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Xenon adsorption-induced flexibility of the zeolitic imidazolate framework ZIF-4 observed by in situ 129Xe NMR spectroscopy

In situ 129Xe NMR spectroscopy reveals an unexpected, xenon adsorption-induced flexibility of ZIF-4. Beyond a certain threshold pressure, xenon induces a structural transition at low temperature. This...

pubs.rsc.org

Emergent Spin‐Glass Behavior in an Iron(II)‐Based Metal–Organic Framework Glass

A one-pot, solvent-free synthesis yields an Fe2+-based metal-organic framework (MOF) glass featuring a continuous random network structure. The material exhibits spin-glass freezing at 14 K, driven b...

advanced.onlinelibrary.wiley.com

Organic flux-mediated ligand exchange enables coordination sphere engineering and topological restructuring in metal-organic framework glasses

Melt-quenched glasses derived from metal-organic frameworks (MOFs) combine the processability of glasses with the modularity and microporosity of MOFs, yet remain structurally and functionally less di...

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Mechanochemical Synthesis Enables Melting, Glass Formation and Glass–Ceramic Conversion in a Cadmium-Based Zeolitic Imidazolate Framework

Metal-organic frameworks (MOFs) are versatile materials with tunable properties and broad applications. Here, we report the first cadmium-based zeolitic imidazolate framework (ZIF) glass, prepared by melt-quenching sub-micrometer-sized Cd(im)2 particles (im– = imidazolate) obtained via mechanochemical synthesis. This route increases defect density and reduces crystallite domain size, lowering the melting temperature from 461 °C (for larger solution-synthesized microcrystals) to 455 °C, thereby mitigating thermal decomposition during melting. Crystalline Cd(im)2 adopts a two-fold interpenetrated diamondoid (dia-c) topology, assembled from tetrahedral Cd2+ centers and im– linkers. Rapid cooling of the Cd(im)2 melt yields a monolithic glass with a glass transition temperature (Tg) of 175 °C. Structural analysis confirms that short-range connectivity within individual networks is maintained, whereas interactions between the interpenetrated networks are disrupted in the glass. Upon reheating, partial recrystallization produces a single-component glass–ceramic with enhanced mechanical properties, an unprecedented behavior in melt-quenched ZIF glasses. Investigations of thermal parameters (cooling rates) and partial linker substitution reveal strategies for tuning the phase behavior of both glass and glass–ceramic. These findings extend ZIF glass systems to second-row transition metal ions and underscore mechanochemical synthesis as a tool for tailoring the thermal properties of MOFs. This dual-phase functionality, combining glassy and crystalline domains of identical composition within a single material, offers potential for applications in thermal energy storage, phase change memory, and optics.

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Defect Identification in Zeolitic Imidazolate Framework Glasses by Solid-State NMR Spectroscopy Using 13CO2 as Probe

Melt-quenched glasses from zeolitic imidazolate frameworks (ZIFs), a subset of metal–organic frameworks (MOFs) constructed from imidazolate linkers and divalent metal ions, represent a novel class of ...

pubs.acs.org

Sodium-Ion-Modified Zeolitic Imidazolate Framework Glasses

Modifying glass compositions is key to creating silicate-based glasses for technologies like optical fibres, catalytic supports, protective coatings, and separation membranes. Here, we extend this con...

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