Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions,Journal of the American Chemical Society

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Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-05-18 00:00:00 , DOI: 10.1021/jacs.7b03144
Zamirbek Akimbekov ₁ , Athanassios D. Katsenis ₂ , G. P. Nagabhushana ₁ , Ghada Ayoub ₂ , Mihails Arhangelskis ₂ , Andrew J. Morris _{3,

4} , Tomislav Friščić ₂ , Alexandra Navrotsky ₁

Affiliation

We provide the first combined experimental and theoretical evaluation of how differences in ligand structure and framework topology affect the relative stabilities of isocompositional (i.e., true polymorph) metal–organic frameworks (MOFs). We used solution calorimetry and periodic DFT calculations to analyze the thermodynamics of two families of topologically distinct polymorphs of zinc zeolitic imidazolate frameworks (ZIFs) based on 2-methyl- and 2-ethylimidazolate linkers, demonstrating a correlation between measured thermodynamic stability and density, and a pronounced effect of the ligand substituent on their stability. The results show that mechanochemical syntheses and transformations of ZIFs are consistent with Ostwald’s rule of stages and proceed toward thermodynamically increasingly stable, more dense phases.

中文翻译：

真正的MOF多晶型物稳定性的实验和理论评估说明了它们的机械化学互变

我们提供了关于配体结构和构架拓扑结构差异如何影响同组成（即，真正的多晶型物）金属-有机构架（MOF）的相对稳定性的首次实验和理论组合评估。我们使用溶液量热法和定期DFT计算来分析基于2-甲基和2-乙基咪唑酯连接基的两个沸石沸石咪唑酸盐骨架（ZIF）拓扑上不同的多晶型物的热力学，证明了测得的热力学稳定性和密度之间的相关性，以及配体取代基对其稳定性的显着影响。结果表明，ZIF的机械化学合成和转变符合奥斯特瓦尔德的阶段规律，并朝着热力学上逐渐稳定，密度更高的阶段发展。

更新日期：2017-06-05

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