Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions

Zamirbek Akimbekov, Athanassios D. Katsenis, G. P. Nagabhushana, Ghada Ayoub, Mihails Arhangelskis, Andrew J. Morris, Tomislav Friščić, Alexandra Navrotsky

Research output: Contribution to journalArticlepeer-review

50 Citations (Scopus)

Abstract

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.
Original languageEnglish
Pages (from-to)7952-7957
JournalJournal of the American Chemical Society
Volume139
Issue number23
Early online date18 May 2017
DOIs
Publication statusPublished - 14 Jun 2017

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