Multivariate zeolitic imidazolate frameworks with an inverting trend in flexibility

Halder, Arijit; Klein, Ryan A.; Lively, Rachel; McGuirk, C. Michael

doi:10.1039/d2cc04362a

Cited by 9 publications

(19 citation statements)

References 29 publications

(38 reference statements)

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“…That is, the stronger these interligand interactions, the more stable the closed phase, and in general, the higher the pressure of a given adsorbate needed to induce the transition. With this insight, the synthetic incorporation of a second ligand that would destabilize the low-porosity closed phase, while simultaneously retaining the topology, flexibility, capacity, and step-shaped adsorption–desorption profile of CdIF-13, was sought …”

Section: Resultsmentioning

confidence: 99%

“…21 2-Methyl-5,6-difluorobenzimidazole (H2M56DFbim, Figure 3a) was chosen as the second ligand for this study, owing to its difluorination, hypothetically amplifying the inverted surface potential and further destabilizing the closed phase, and thermal stability suitable for solvothermal synthesis conditions. 28 CdIF-13 is synthesized using prototypical solvothermal conditions, wherein Cd(ClO 4 ) 2 •xH 2 O and benzimidazole (HBim) are mixed in N,N-dimethylformamide (DMF) and heated overnight (≈16 h) at 130 °C (Figure 1d). DMFsolvated CdIF-13 can then be fully activated by washing with dichloromethane (CH 2 Cl 2 ) and heating under reduced pressure.…”

Section: ■ Introductionmentioning

confidence: 99%

“…27,28 A series of crystalline flexible frameworks were synthesized; however, at ratios lower than 14:1 bim − /2M56DFbim − , the materials display decreased useable capacities because they do not achieve the fully closed P1̅ structure (Figures S6 and S7). 28 As such, we selected the 14:1 material for the current detailed hydrogen adsorption study.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The 14:1 bim − /2M56DFbim − derivative (sod-Cd-(bim) 1.87 (2M56DFbim) 0.13 ), as determined by post-digestion solution-phase 1 H NMR spectroscopy (Figures S6 and S7), fortunately retains each key feature of CdIF-13, in addition to exhibiting a significantly reduced adsorption threshold pressure for propane at 25 °C (Figures 1e,f, 3b,c, and S9). 28 Pawley fits of the PXRD patterns for the as-synthesized (i.e., DMFsolvated) and activated frameworks indicated both the retention of the sod topology and the phase change to a similar lowered porosity closed state upon solvent removal (Figures 3b and S30). Quite excitingly, while retaining the adsorption capacity and shape of CdIF-13, the step threshold pressure for C 3 H 8 at 25 °C was reduced from ≈20 mbar for CdIF-13 to ≈5 mbar (Figures 1f, 3c, and S9).…”

Section: ■ Introductionmentioning

confidence: 99%

“…This thermodynamic requirement, compounded by the still serendipitous discovery of flexible frameworks, has severely hindered the development of next-generation H 2 storage materials. Therefore, a chemically intuitive approach to lowering the endothermic penalty for the phase change in known flexible frameworks would open the door to new possibilities in H 2 storage and delivery. ,, One such approach is the multivariate, or mixed linker, approach, which has very recently been used to tune the adsorption threshold pressure in strongly adsorbing gases like propane and acetylene . However, this approach has not been explored for enabling step-shaped adsorption of weakly adsorbing gases like H 2 .…”

Section: Introductionmentioning

confidence: 99%

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Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process

et al. 2023

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Step-shaped adsorption–desorption of gaseous payloads by flexible metal–organic frameworks can facilitate the delivery of large usable capacities with significantly reduced energetic penalties. This is desirable for the storage, transport, and delivery of H2, as prototypical adsorbents require large swings in pressure and temperature to achieve usable capacities approaching their total capacities. However, the weak physisorption of H2 typically necessitates undesirably high pressures to induce the framework phase change. As de novo design of flexible frameworks is exceedingly challenging, the ability to intuitively adapt known frameworks is required. We demonstrate that the multivariate linker approach is a powerful tool for tuning the phase change behavior of flexible frameworks. In this work, 2-methyl-5,6-difluorobenzimidazolate was solvothermally incorporated into the known framework CdIF-13 (sod-Cd(benzimidazolate)2), resulting in the multivariate framework sod-Cd(benzimidazolate)1.87(2-methyl-5,6-difluorobenzimidazolate)0.13 (ratio = 14:1), which exhibited a considerably reduced stepped adsorption threshold pressure while maintaining the desirable adsorption–desorption profile and capacity of CdIF-13. At 77 K, the multivariate framework exhibits stepped H2 adsorption with saturation below 50 bar and minimal desorption hysteresis at 5 bar. At 87 K, saturation of step-shaped adsorption occurs by 90 bar, with hysteresis closing at 30 bar. These adsorption–desorption profiles enable usable capacities in a mild pressure swing process above 1 mass %, representing 85–92% of the total capacities. This work demonstrates that the desirable performance of flexible frameworks can be readily adapted through the multivariate approach to enable efficient storage and delivery of weakly physisorbing species.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process

et al. 2023

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Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs

Thaggard,

Kankanamalage,

Park

et al. 2024

Advanced Materials

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Photochromic materials with properties that can be dynamically tailored as a function of external stimuli are a rapidly expanding field driven by applications in areas ranging from molecular computing, nanotechnology, or photopharmacology to programable heterogeneous catalysis. Challenges arise, however, when translating the rapid, solution‐like response of stimuli‐responsive moieties to solid‐state materials due to the intermolecular interactions imposed through close molecular packing in bulk solids. As a result, the integration of photochromic compounds into synthetically programable porous matrices, such as metal‐organic frameworks (MOFs), has come to the forefront as an emerging strategy for photochromic material development. This review highlights how the core principles of reticular chemistry (on the example of MOFs) play a critical role in the photochromic material performance, surpassing the limitations previously observed in solution or solid state. The symbiotic relationship between photoresponsive compounds and porous frameworks with a focus on how reticular synthesis creates avenues toward tailorable photoisomerization kinetics, directional energy and charge transfer, switchable gas sorption, and synergistic chromophore communication is discussed. This review not only focuses on the recent cutting‐edge advancements in photochromic material development, but also highlights novel, vital‐to‐pursue pathways for multifaceted functional materials in the realms of energy, technology, and biomedicine.

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Multivariate Flexible Metal–Organic Frameworks and Covalent Organic Frameworks

Sobczak,

Drwęska,

Gromelska

et al. 2024

Small

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Precise control of the void environment, achieved through multiple functional groups and enhanced by structural adaptations to guest molecules, stands at the forefront of scientific inquiry. Flexible multivariate open framework materials (OFMs), including covalent organic frameworks and metal–organic frameworks, meet these criteria and are expected to play a crucial role in gas storage and separation, pollutant removal, and catalysis. Nevertheless, there is a notable lack of critical evaluation of achievements in their chemistry and future prospects for their development or implementation. To provide a comprehensive historical context, the initial discussion explores into the realm of “classical” flexible OFMs, where their origin, various modes of flexibility, similarities to proteins, advanced tuning methods, and recent applications are explored. Subsequently, multivariate flexible materials, the methodologies involved in their synthesis, and horizons of their application are focussed. Furthermore, the reader to the concept of spatial distribution is introduced, providing a brief overview of the latest reports that have contributed to its elucidation. In summary, the critical review not only explores the landscape of multivariate flexible materials but also sheds light on the obstacles that the scientific community must overcome to fully unlock the potential of this fascinating field.

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Multivariate zeolitic imidazolate frameworks with an inverting trend in flexibility

Abstract: Modulative adsorption behaviour with an inverting stepped adsorption pressure is observed in a family of multivariate flexible frameworks.

Cited by 9 publications

References 29 publications

Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process

Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process

Switching from Molecules to Functional Materials: Breakthroughs in Photochromism With MOFs

Multivariate Flexible Metal–Organic Frameworks and Covalent Organic Frameworks

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