Identification of a metastable uranium metal-organic framework isomer through non-equilibrium synthesis.

Autor:	Hanna SL; Department of Chemistry and International Institute for Nanotechnology, Northwestern University Evanston IL 60208 USA o-farha@northwestern.edu., Debela TT; Department of Chemistry and Biochemistry, University of Oregon Eugene OR 97403 USA chendon@uoregon.edu., Mroz AM; Department of Chemistry and Biochemistry, University of Oregon Eugene OR 97403 USA chendon@uoregon.edu., Syed ZH; Department of Chemistry and International Institute for Nanotechnology, Northwestern University Evanston IL 60208 USA o-farha@northwestern.edu., Kirlikovali KO; Department of Chemistry and International Institute for Nanotechnology, Northwestern University Evanston IL 60208 USA o-farha@northwestern.edu., Hendon CH; Department of Chemistry and Biochemistry, University of Oregon Eugene OR 97403 USA chendon@uoregon.edu.; Materials Science Institute, University of Oregon Eugene OR 97403 USA., Farha OK; Department of Chemistry and International Institute for Nanotechnology, Northwestern University Evanston IL 60208 USA o-farha@northwestern.edu.; Department of Chemical and Biological Engineering, Northwestern University Evanston IL 60208 USA.
Jazyk:	angličtina
Zdroj:	Chemical science [Chem Sci] 2022 Oct 31; Vol. 13 (44), pp. 13032-13039. Date of Electronic Publication: 2022 Oct 31 (Print Publication: 2022).
DOI:	10.1039/d2sc04783g
Abstrakt:	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. Competing Interests: O. K. F. has a financial interest in NuMat Technologies, a startup company that is seeking to commercialize MOFs. All other authors declare no competing interests. (This journal is © The Royal Society of Chemistry.)
Databáze:	MEDLINE
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