Abstract
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 language | English |
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Pages (from-to) | 3777-3783 |
Number of pages | 7 |
Journal | Chemistry of Materials |
Volume | 31 |
Issue number | 10 |
Early online date | 24 Apr 2019 |
DOIs | |
Publication status | Published - 28 May 2019 |
ASJC Scopus subject areas
- General Chemistry
- General Chemical Engineering
- Materials Chemistry
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