Exploiting <i>in situ</i> NMR to monitor the formation of a metal–organic framework

Jones, Carl J.; Hughes, Colan E.; Yeung, Hamish H.‐M.; Paul, Alison; Harris, Kenneth D. M.; Easun, Timothy L.

doi:10.1039/d0sc04892e

Cited by 23 publications

(20 citation statements)

References 60 publications

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“…Besides aluminophosphates and zeolites, several attempts were devoted to the investigation of MOF materials. [73][74][75] Table 5 establishes a cross-reference index between the materials studied, the experimental approaches used, the mechanistic information obtained and the corresponding literature sources. The results show that the liquid state approach was applied mainly to AlPO 4 and MOF materials.…”

Section: Application Of In Situ Mas Nmr For Mechanistic Studies Of Hydrothermal Synthesis Of Zeolitesmentioning

confidence: 99%

Application of Multinuclear MAS NMR for the in situ Monitoring of Hydrothermal Synthesis of Zeolites

Иванова

Kolyagin

2021

Chemistry A European J

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Section: Application Of In Situ Mas Nmr For Mechanistic Studies Of Hydrothermal Synthesis Of Zeolitesmentioning

confidence: 99%

Application of Multinuclear MAS NMR for the in situ Monitoring of Hydrothermal Synthesis of Zeolites

Иванова

Kolyagin

2021

Chemistry A European J

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“…In UiO-66, growth has been observed to occur via the addition of building units, and there is evidence to support that an amorphous-to-crystalline rearrangement may be involved . Other investigations also suggest that MOF synthesis involves solid-to-solid rearrangements ,, or the generation of intermediates, which undergo Ostwald step changes to arrive at a certain phase. − Despite mechanistic differences in nucleation and growth, the vast majority of MOFs contain linkers involving exclusively carboxylate coordination chemistry and the p K a differences between coordinating groups are minor. By contrast, the MOF-74 family of MOFs is built from 2,5-dioxido-1,4-benzenedicarboxylate (H 4 DOBDC in protonated form), where both the aryloxide and carboxylate coordinate to the metal (Figure ).…”

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confidence: 99%

Linker Deprotonation and Structural Evolution on the Pathway to MOF-74

et al. 2022

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The synthesis of MOF-74 (MOF = metal−organic framework) proceeds first through the generation of chemically and topologically distinct materials, referred to as phases, displaying exclusively carboxylate coordination, followed by further deprotonation to enable oxo coordination and MOF-74 formation. The synthesis of Mg-MOF-74 at high concentrations of linker and metal enables the stabilization and characterization of the previously unobserved, exclusively carboxylate coordinating phases. Ex situ and in situ approaches are leveraged to provide the time-resolved observation of Mg-MOF-74 synthesis and the formation of phases that precede Mg-MOF-74 formation as well as metastable phase dissolution. These data support dissolution and redeposition as the mechanism of MOF-74 formation and provide insight into the formation mechanism of MOFs with multiple linker coordination types.

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“…Furthermore, a different solvent (DMF) can significantly affect the energetics of conformational transformations of the solute. , In this context, we can assess the effect of guest molecules on the collective assembly of half-SBUs. Finally, there is experimental evidence that studying the solution in the early stages of assembly can significantly improve our understanding of the mechanism of MOF synthesis …”

Section: Methodsmentioning

confidence: 99%

“…Finally, there is experimental evidence that studying the solution in the early stages of assembly can significantly improve our understanding of the mechanism of MOF synthesis. 79 Calculation of Rates. We calculate the nucleation and growth rates of cluster formation during self-assembly following the approach discussed by Yuhara et al 80 In more detail, we calculate rates per unit volume, J.…”

Section: ■ Introductionmentioning

confidence: 99%

Understanding Metal–Organic Framework Nucleation from a Solution with Evolving Graphs

et al. 2022

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A mechanistic understanding of metal−organic framework (MOF) synthesis and scale-up remains underexplored due to the complex nature of the interactions of their building blocks. In this work, we investigate the collective assembly of building units at the early stages of MOF nucleation, using MIL-101(Cr) as a prototypical example. Using large-scale molecular dynamics simulations, we observe that the choice of solvent (water and N,N-dimethylformamide), the introduction of ions (Na + and F − ) and the relative populations of MIL-101(Cr) half-secondary building unit (half-SBU) isomers have a strong influence on the cluster formation process. Additionally, the shape, size, nucleation and growth rates, crystallinity, and short and long-range order largely vary depending on the synthesis conditions. We evaluate these properties as they naturally emerge when interpreting the self-assembly of MOF nuclei as the time evolution of an undirected graph. Solution-induced conformational complexity and ionic concentration have a dramatic effect on the morphology of clusters emerging during assembly. While pure solvents lead to the rapid formation of a small number of large clusters, the presence of ions in aqueous solutions results in smaller clusters and slower nucleation. This diversity is captured by the key features of the graph representation. Principle component analysis on graph properties reveals that only a small number of molecular descriptors is needed to deconvolute MOF self-assembly. Descriptors such as the average coordination number between half-SBUs and fractal dimension are of particulalr interest as they can be can be followed experimentally by techniques like by time-resolved spectroscopy. Ultimately, graph theory emerges as an approach that can be used to understand complex processes revealing molecular descriptors accessible by both simulation and experiment.

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Exploiting in situ NMR to monitor the formation of a metal–organic framework

Abstract: The formation processes of metal-organic frameworks are becoming more widely researched using in-situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis...

Cited by 23 publications

References 60 publications

Application of Multinuclear MAS NMR for the in situ Monitoring of Hydrothermal Synthesis of Zeolites

Application of Multinuclear MAS NMR for the in situ Monitoring of Hydrothermal Synthesis of Zeolites

Linker Deprotonation and Structural Evolution on the Pathway to MOF-74

Understanding Metal–Organic Framework Nucleation from a Solution with Evolving Graphs

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