The growth of metal-organic frameworks (MOFs) is most frequently accessed by the direct assembly of metal cations and multitopic ready-to-connect ligands under solvothermal conditions. However, such nonambient conditions are expected to impose a synthetic challenge to incorporate degradable ligands into MOFs. This explains why imine-based MOFs are scarce as the imine motif is usually prone to decompose through hydrolysis. This work not only showcases mechanochemistry as an ambient, sustainable, and high-yield strategy for synthesizing a variety of imine-based MOFs but also achieves the integration of ligand synthesis and MOF growth into a single tandem step. Thus, this work provides straightforward access to imine-based MOFs, a subfamily of historically challenging MOF materials.
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http://dx.doi.org/10.1021/jacs.5c00460 | DOI Listing |
J Am Chem Soc
March 2025
Department of Chemistry and Biochemistry, and Nanoscale & Quantum Phenomena Institute, Ohio University, Athens, Ohio 45701, United States.
The growth of metal-organic frameworks (MOFs) is most frequently accessed by the direct assembly of metal cations and multitopic ready-to-connect ligands under solvothermal conditions. However, such nonambient conditions are expected to impose a synthetic challenge to incorporate degradable ligands into MOFs. This explains why imine-based MOFs are scarce as the imine motif is usually prone to decompose through hydrolysis.
View Article and Find Full Text PDFInorg Chem
January 2020
Technische Universität Dresden, Chair of Inorganic Chemistry , Bergstraße 66 , D-01062 Dresden , Germany.
formation of imine-based organic linkers facilitates the formation of metal-organic frameworks (MOFs), in particular if linker solubility hampers the direct synthesis. The reaction of ZrCl with 4-formylbenzoic acid or 4-formyl-3-hydroxybenzoic acid as the aldehyde source and 4-aminobenzoic acid as the amine source is shown to produce zirconium MOFs isoreticular to UiO-66 (PCN-161 and a novel DUT-133, [ZrO(OH)(CHNO)], respectively). A similar reaction with -phenylenediamine as the amine-containing building block gave 2-fold interpenetrated framework (PCN-164).
View Article and Find Full Text PDFJ Am Chem Soc
September 2019
Department of Chemistry , Texas A&M University , College Station, Texas 77843-3255 , United States.
Sophisticated chemical processes widely observed in biological cells require precise apportionment regulation of building units, which inspires researchers to develop tailorable architectures with controllable heterogeneity for replication, recognition and information storage. However, it remains a substantial challenge to endow multivariate materials with internal sequences and controllable apportionments. Herein, we introduce a novel strategy to manipulate the apportionment of functional groups in multivariate metal-organic frameworks (MTV-MOFs) by preincorporating interlocked linkers into framework materials.
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