Structural studies of metal–organic frameworks under high pressure

McKellar, Scott C.; Moggach, Stephen A.

doi:10.1107/s2052520615018168

Cited by 91 publications

(107 citation statements)

References 198 publications

(227 reference statements)

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“…Unlike MOF‐1 a , MOF‐1 b catalyzed the reactions of terminal propargylamines with widths less than 4.2 Å under CO 2 (0.5 MPa) at 60 °C (Table S5 in the Supporting Information). Such catalytic selectivity results have proved the existence of porosity of MOF‐1 b under high pressure (0.5 MPa), which is consistent with the adsorption analysis for MOF‐1 b . The experimental results perfectly illustrate that MOF‐1 a is a flexible and switchable catalyst with catalytic selectivity of substrates, similarly to sophisticated biological systems.…”

Section: Resultsmentioning

confidence: 99%

Efficient and Reusable Metal–Organic Framework Catalysts for Carboxylative Cyclization of Propargylamines with Carbon Dioxide

et al. 2017

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Carbon dioxide (CO2) capture and transformation are important for decreasing the concentration of atmospheric CO2. To effectively capture CO2 and further fix it into valuable chemical products, functionalized dynamic metal–organic frameworks (MOFs) have been utilized not only because of their inherent cavity for accommodating CO2 but also owing to their reversible structural transformations in response to external stimuli for regulating the reaction. Herein, we report a dynamic and functional MOF [Cd3(L)2(BDC)3]2⋅16 DMF (MOF‐1 a; DMF=N,N‐dimethylformamide) achieved by reaction of the amino tripodal imidazole ligand N1‐(4‐(1 H‐imidazol‐1‐yl)benzyl)‐N1‐ (2‐aminoethyl)ethane‐1,2‐diamine (L) and 1,4‐benzenedicarboxylic acid (H2BDC) with cadmium salt. MOF‐1 a not only shows unprecedented high catalytic activity [initial turnover number (TON) up to 9300] and broad substrate scope for the carboxylative cyclization of propargylamines with CO2, but also can be switched on and off upon reversible structural transformation owing to its dynamic five‐fold interpenetrating structure. Further studies demonstrate that MOF‐1 a shows selective catalytic properties depending on the size of substrates, similarly to sophisticated biological systems.

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Section: Resultsmentioning

confidence: 99%

Efficient and Reusable Metal–Organic Framework Catalysts for Carboxylative Cyclization of Propargylamines with Carbon Dioxide

et al. 2017

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“…Although higher K values have been reported, these are not directly related to the compression of the framework but to the penetration of the PTM into the pores that increases the stability of the system at low-P regimes. 24 When it comes to non-porous (dense) MOFs, the compressibility of Zn(GlyTyr)2 is substantially higher than those reported for very stable zeolite-type materials like Zn(Im)2-zni (14 GPa) 23 and LiB(Im)4 (16.6 GPa). 25 Also, these last display smaller changes in the volume cell at the higher pressures studied (below 10%).…”

Section: High-pressure Structural Transformation In a Single Crystalmentioning

confidence: 94%

Peptide metal–organic frameworks under pressure: flexible linkers for cooperative compression

et al. 2018

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We investigate the structural response of a dense peptide metal-organic framework using in situ powder and single-crystal X-ray diffraction under high-pressures. Crystals of Zn(GlyTyr) show a reversible compression by 13% in volume at 4 GPa that is facilitated by the ability of the peptidic linker to act as a flexible string for a cooperative response of the structure to strain. This structural transformation is controlled by changes to the conformation of the peptide, which enables a bond rearrangement in the coordination sphere of the metal and changes to the strength and directionality of the supramolecular interactions specific to the side chain groups in the dipeptide sequence. Compared to other structural transformations in Zn(ii) peptide MOFs, this behaviour is not affected by host/guest interactions and relies exclusively on the conformational flexibility of the peptide and its side chain chemistry.

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“…Of course, this task would be easier if we knew how they respond to harsh pressure conditions. Although MOFs are still relatively little explored at high‐pressure, some examples of robust frameworks, like ZIF‐8 and ammonium metal formates, are already known, and their compression behavior can be studied by in situ diffraction . By analyzing MOFs response to pressures which can push their resistance to the limit we could get precious information for the design of more robust frameworks with potential applications in high‐pressure processes.…”

Section: Organized Materials By High‐pressure Confinementmentioning

confidence: 99%

“…Although MOFs are still relatively little explored at high-pressure, some examples of robust frameworks, like ZIF-8 [610] and ammonium metal formates, [754] are already known, and their compression behavior can be studied by in situ diffraction. [755] By analyzing MOFs response to pressures which can push their resistance to the limit we could get precious information for the design of more robust frameworks with potential applications in highpressure processes. A recent example is the "retrofitting" of MOF-520 (that amorphizes at 2.81 GPa) with an extra bridging ligand, which allows the retrofitted material to remain crystalline up to 5.5 GPa (Figure 55).…”

Section: High-pressure and Mofsmentioning

confidence: 99%

Supramolecular Organization in Confined Nanospaces

Tabacchi

2018

ChemPhysChem

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Empty spaces are abhorred by nature, which immediately rushes in to fill the void. Humans have learnt pretty well how to make ordered empty nanocontainers, and to get useful products out of them. When such an order is imparted to molecules, new properties may appear, often yielding advanced applications. This review illustrates how the organized void space inherently present in various materials: zeolites, clathrates, mesoporous silica/organosilica, and metal organic frameworks (MOF), for example, can be exploited to create confined, organized, and self-assembled supramolecular structures of low dimensionality. Features of the confining matrices relevant to organization are presented with special focus on molecular-level aspects. Selected examples of confined supramolecular assemblies - from small molecules to quantum dots or luminescent species - are aimed to show the complexity and potential of this approach. Natural confinement (minerals) and hyperconfinement (high pressure) provide further opportunities to understand and master the atomistic-level interactions governing supramolecular organization under nanospace restrictions.

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Structural studies of metal–organic frameworks under high pressure

Cited by 91 publications

References 198 publications

Efficient and Reusable Metal–Organic Framework Catalysts for Carboxylative Cyclization of Propargylamines with Carbon Dioxide

Efficient and Reusable Metal–Organic Framework Catalysts for Carboxylative Cyclization of Propargylamines with Carbon Dioxide

Peptide metal–organic frameworks under pressure: flexible linkers for cooperative compression

Supramolecular Organization in Confined Nanospaces

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