Fluoro-Bridged Clusters in Rare-Earth Metal–Organic Frameworks

Vizuet, Juan P.; Mortensen, Marie L.; Lewis, Abigail L.; Wunch, Melissa A.; Firouzi, Hamid R; McCandless, Gregory T.; Balkus, Kenneth J.

doi:10.1021/jacs.1c10493

Cited by 49 publications

(95 citation statements)

References 76 publications

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“…HIAM-3905 and HIAM-3906 are fluoro-bridged clusters, Y 6 (F 8 )(COO) 8 and Y 6 (F 8 )(COO) Figure4a2 and 4b2), which is consistent with the recent reported work that using μ 3 -F rather than μ 3 -O will offer a much better crystallographic fit when 2-fluorobenzoic acid was employed as the modulator 58. The fluorine presence in HIAM-3905 and HIAM-3906 were confirmed by SEM-EDS analysis (FigureS5-S6).Characterization of amino group induced NIR emissive Y-MOFs.The single crystals of HIAM-3905 and HIAM-3906 show red and dark red emissions with a peak maximum at 665 nm and 689 nm, which are 144 nm and 168 nm bathochromic shifts compared with that of HIAM-3901 (Figure5b), confirming that amino group has the capacity to red-shift the emission energy/wavelength.…”

supporting

confidence: 90%

Amino group induced structural diversity and near-infrared emission of yttrium-tetracarboxylate frameworks

et al. 2022

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supporting

confidence: 90%

Amino group induced structural diversity and near-infrared emission of yttrium-tetracarboxylate frameworks

et al. 2022

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“…However, the conventional metal-oxo SBUs in carboxylate-based MOFs have very confined carrier mobility and charge transport properties 20 , 21 . Very few MOFs have been reported to occupy halide-bridged SBUs, until the very recent discovery of UiO-66 type MOFs with fluoro bridging groups 22 .…”

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confidence: 99%

Bromo- and iodo-bridged building units in metal-organic frameworks for enhanced carrier transport and CO2 photoreduction by water vapor

et al. 2022

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Organolead halide hybrids have many promising attributes for photocatalysis, e.g. tunable bandgaps and excellent carrier transport, but their instability constraints render them vulnerable to polar molecules and limit their photocatalysis in moisture. Herein, we report the construction of metal–organic frameworks based on [Pb2X]3+ (X = Br–/I–) chains as secondary building units and 2-amino-terephthalate as organic linkers, and extend their applications in photocatalytic CO2 reduction with water vapor as the reductant. Hall effect measurement and ultrafast transient absorption spectroscopy demonstrate the bromo/iodo-bridged frameworks have substantially enhanced photocarrier transport, which results in photocatalytic performances superior to conventional metal-oxo metal-organic frameworks. Moreover, in contrast to lead perovskites, the [Pb2X]3+-based frameworks have accessible porosity and high moisture stability for gas-phase photocatalytic reaction between CO2 and H2O. This work significantly advances the excellent carrier transport of lead perovskites into the field of metal-organic frameworks.

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“… 23 A recent manuscript by Vizuet et al reported the possible presence of fluoro bridging groups in metal clusters of Ho-UiO-66 analogues, which they attributed to the use of a fluorinated modulator. 26 …”

Section: Introductionmentioning

confidence: 99%

Dramatic Enhancement of Rare-Earth Metal–Organic Framework Stability Via Metal Cluster Fluorination

Christian

Fritzsching

Harvey

et al. 2022

JACS Au

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Rare-earth polynuclear metal–organic frameworks (RE-MOFs) have demonstrated high durability for caustic acid gas adsorption and separation based on gas adsorption to the metal clusters. The metal clusters in the RE-MOFs traditionally contain RE metals bound by μ 3 –OH groups connected via organic linkers. Recent studies have suggested that these hydroxyl groups could be replaced by fluorine atoms during synthesis that includes a fluorine-containing modulator. Here, a combined modeling and experimental study was undertaken to elucidate the role of metal cluster fluorination on the thermodynamic stability, structure, and gas adsorption properties of RE-MOFs. Through systematic density-functional theory calculations, fluorinated clusters were found to be thermodynamically more stable than hydroxylated clusters by up to 8–16 kJ/mol per atom for 100% fluorination. The extent of fluorination in the metal clusters was validated through a 19 F NMR characterization of 2,5-dihydroxyterepthalic acid (Y-DOBDC) MOF synthesized with a fluorine-containing modulator. 19 F magic-angle spinning NMR identified two primary peaks in the isotropic chemical shift (δ iso ) spectra located at −64.2 and −69.6 ppm, matching calculated 19 F NMR δ iso peaks at −63.0 and −70.0 ppm for fluorinated systems. Calculations also indicate that fluorination of the Y-DOBDC MOF had negligible effects on the acid gas (SO 2 , NO 2 , H 2 O) binding energies, which decreased by only ∼4 kJ/mol for the 100% fluorinated structure relative to the hydroxylated structure. Additionally, fluorination did not change the relative gas binding strengths (SO 2 > H 2 O > NO 2 ). Therefore, for the first time the presence of fluorine in the metal clusters was found to significantly stabilize RE-MOFs without changing their acid-gas adsorption properties.

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Fluoro-Bridged Clusters in Rare-Earth Metal–Organic Frameworks

Cited by 49 publications

References 76 publications

Amino group induced structural diversity and near-infrared emission of yttrium-tetracarboxylate frameworks

Amino group induced structural diversity and near-infrared emission of yttrium-tetracarboxylate frameworks

Bromo- and iodo-bridged building units in metal-organic frameworks for enhanced carrier transport and CO2 photoreduction by water vapor

Dramatic Enhancement of Rare-Earth Metal–Organic Framework Stability Via Metal Cluster Fluorination

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