Identification of a metastable uranium metal–organic framework isomer through non-equilibrium synthesis. Issue 44 (31st October 2022)

• Record Type: Journal Article
• Authors: Hanna, Sylvia L.; Debela, Tekalign T.; Mroz, Austin M.; Syed, Zoha H.; Kirlikovali, Kent O.; Hendon, Christopher H.; Farha, Omar K.
• Is Part Of: Chemical science. Volume 13:Issue 44(2022)
• Page Start: 13032
• Page End: 13039
• Publication Date: 2022-10-31
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc04783g
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Identifying the relationship between structure and energetics in a uranium MOF isomer system reveals how non-equilibrium synthetic conditions can be used as a strategy to target metastable MOFs. Abstract : Since the structure of supramolecular isomers determines their performance, rational synthesis of a specific isomer hinges on understanding the energetic relationships between isomeric possibilities. To this end, we have systematically interrogated a pair of uranium-based metal–organic framework topological isomers both synthetically and through density functional theory (DFT) energetic calculations. Although synthetic and energetic data initially appeared to mismatch, we assigned this phenomenon to the appearance of a metastable isomer, driven by levers defined by Le Châtelier's principle. Identifying the relationship between structure and energetics in this study reveals how non-equilibrium synthetic conditions can be used as a strategy to target metastable MOFs. Additionally, this study demonstrates how defined MOF design rules may enable access to products within the energetic phase space which are more complex than conventional binary ( e.g., kinetic vs. thermodynamic) products.