Metal–Organic Crystallized Glasses: Microstructure Formation and Their Properties

作者：Soracha Kosasang, Nattapol Ma, David Christensen, Morten M. Smedskjær, Hiroki Yamada, Satoshi Horike · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c10513 · 被引用次数：6 · 研究领域：Glass properties and applications、Metal-Organic Frameworks: Synthesis and Applications、Luminescence Properties of Advanced Materials

Partial crystallization within a glass matrix to form microcrystalline domains offers a pathway to glass-ceramic materials with properties distinct from those of both the parent glass and crystalline phases. This concept has been limited to inorganic glasses. Here, we introduce metal–organic crystallized glasses (MOCGs), prepared by controlling the crystallization process within metal–organic framework (MOF) glasses, and explore their properties. By adjusting the annealing temperature and duration above the glass transition temperature ( T g ), we control the crystallinity and crystallite size in 2D Cd(H 2 PO 4 ) 2 (1,2,4-triazole) 2 -based MOCGs, enabling modulation of their micromechanical properties, dielectric constants, and proton conductivities. The MOCG with a 15% relative crystallinity exhibits a dielectric constant of 3.3 × 10 2 at 100 kHz, an order of magnitude higher than that of both the parent glass and crystalline phases across 30–100 °C. We further extend this concept to a mixed-metal MOF glass system, where solid solutions occur through the incorporation of Cd 2+ and Mn 2+ ions from the amorphous matrix into crystallizing lattices upon annealing.