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Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
An Exceptionally Stable Metal-Organic Framework Constructed from Chelate-Based Metal-Organic Polyhedra
Jerika A Chiong1, Jie Zhu1, Jake B Bailey1
1Department of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, California 92093, United States.
Abstract:
We report the rational design and synthesis of a water-stable metal-organic framework (MOF), Fe-HAF-1, constructed from supramolecular, Fe3+-hydroxamate-based polyhedra with mononuclear metal nodes. Owing to its chelate-based construction, Fe-HAF-1 displays exceptional chemical stability in organic and aqueous solvents over a wide pH range (pH 1-14), including in the presence of 5 M NaOH. Despite the charge neutrality of the Fe3+-tris(hydroxamate) centers, Fe-HAF-1 crystals are negatively charged above pH 4. This unexpected property is attributed to the formation of defects during crystallization that results in uncoordinated hydroxamate ligands or hydroxide-coordinated Fe centers. The anionic nature of Fe-HAF-1 crystals enables selective adsorption of positively charged ions in aqueous solution, resulting in efficient separation of organic dyes and other charged species in a size-selective fashion. Fe-HAF-1 presents a new addition to a small group of chelate-based MOFs and provides a rare framework whose 3D connectivity is exclusively formed by metal-hydroxamate coordination.
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