Theoretical prediction and experimental evaluation of topological landscape and thermodynamic stability of a fluorinated zeolitic imidazolate framework
Research output: Contribution to journal › Article › peer-review
Colleges, School and Institutes
- 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.
|Number of pages||7|
|Journal||Chemistry of Materials|
|Early online date||24 Apr 2019|
|Publication status||Published - 28 May 2019|