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Structural Flexibility Driven Crystal-to-Glass Transition and Long-Afterglow in Mechanochemically Synthesized Zn(II) Hybrids
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DOI：10.1002/adom.71599.png)
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Abstract
En 中文
Achieving controllable vitrification in organic-inorganic metal halides (OIMHs) without luminescence quenching remains a challenge due to rigid structural constraints. Herein, we exploit the structural flexibility inherent in 0D Zn(II) hybrids to develop a mechanochemical strategy for coordination-engineered long-afterglow materials. By simply modulating liquid-assisted grinding (LAG) agents, we achieve precise interconversion between halide-coordinated [ZnX4]2− and coordination-type [ZnNX3]2− geometries. Crucially, this flexible coordination environment facilitates a crystal-to-glass transition (Tg = 51.1°C –65.1°C) while preserving luminescent integrity. The resulting materials exhibit tunable room-temperature phosphorescence (3.6–11.7 ms), with (IMP)ZnCl3 showing a persistent yellow afterglow. Density functional theory (DFT) calculations reveal that halogen substitution and coordination geometry synergistically regulate charge-transfer processes. This work establishes a structure-flexibility-luminescence relationship, enabling dynamic anti-counterfeiting systems based on time-resolved optical logic.
Keywords:
0D organic-inorganic metal halides
anti-counterfeiting
mechanochemical synthesis
photoluminescence
Zn(II)-based luminescent glass
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