Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions.
Katsenis, Athanassios D
Journal of the American Chemical Society
American Chemical Society
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Akimbekov, Z., Katsenis, A. D., Nagabhushana, G., Ayoub, G., Arhangelskis, M., Morris, A., Friščić, T., & et al. (2017). Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechanochemical Interconversions.. Journal of the American Chemical Society, 139 7952-7957. https://doi.org/10.1021/jacs.7b03144
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.
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.
External DOI: https://doi.org/10.1021/jacs.7b03144
This record's URL: https://www.repository.cam.ac.uk/handle/1810/265000
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