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

Accepted version
Peer-reviewed

Type

Article

Change log

Authors

Akimbekov, Z 
Katsenis, AD 
Nagabhushana, GP 
Ayoub, G 
Arhangelskis, Mihails  ORCID logo  https://orcid.org/0000-0003-1150-3108

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.

Description

Keywords

0306 Physical Chemistry (incl. Structural)

Journal Title

Journal of the American Chemical Society

Conference Name

Journal ISSN

0002-7863
1520-5126

Volume Title

139

Publisher

American Chemical Society
Sponsorship
Support for calorimetry was provided by the U.S. Department of Energy, Grant DE-SC0016573. We acknowledge the financial support of the NSERC Strategic Grant STPGP 463405-14. A.D.K. acknowledges support by the FRQNT Postdoctoral Scholarship. We are grateful for computational support from the UK national high performance computing service, ARCHER, for which access was obtained via the UKCP consortium and funded by EPSRC Grant Ref EP/K013564/1.
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