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

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 (T_g) 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.