Theoretical prediction and experimental evaluation of topological landscape and thermodynamic stability of a fluorinated zeolitic imidazolate framework

Research output: Contribution to journalArticlepeer-review


  • Mihails Arhangelskis
  • Athanassios D. Katsenis
  • Novendra Novendra
  • Zamirbek Akimbekov
  • Dayaker Gandrath
  • Joseph M. Marrett
  • Ghada Ayoub
  • Omar K. Farha
  • Tomislav Friščić
  • Alexandra Navrotsky

Colleges, School and Institutes

External organisations

  • McGill University
  • UC Davis
  • Northwestern University, Chicago, IL.


The prediction of topological preferences and polymorph stability remains a challenge for the design of metal-organic frameworks exhibiting a rich topological landscape, such as zeolitic imidazolate frameworks (ZIFs). Here, we have used mechanochemical screening and calorimetry to test the ability of dispersion-corrected periodic density functional theory (DFT) to accurately survey the topological landscape, as well as quantitatively evaluate polymorph stability, for a previously not synthesized ZIF composition. Theoretical calculations were used to obtain an energy ranking and evaluate energy differences for a set of hypothetical, topologically distinct structures of a fluorine-substituted ZIF. Calculations were then experimentally validated via mechanochemical screening and calorimetry, which confirmed two out of three theoretically anticipated topologies, including a fluorinated analogue of the popular ZIF-8, while revealing an excellent match between the measured and theoretically calculated energetic differences between them. The results, which speak strongly in favor of the ability of dispersion-corrected periodic DFT to predict the topological landscape of new ZIFs, also reveal the ability to use peripheral substituents on the organic linker to modify the framework thermodynamic stability.


Original languageEnglish
Pages (from-to)3777-3783
Number of pages7
JournalChemistry of Materials
Issue number10
Early online date24 Apr 2019
Publication statusPublished - 28 May 2019