Reversible Switching between Nonporous and Porous Phases of a New SIFSIX Coordination Network Induced by a Flexible Linker Ligand

Song, Bai‐Qiao; Yang, Qingyuan; Wang, Shiqiang; Vandichel, Matthias; Kumar, Amrit; Crowley, Clare M.; Kumar, Naveen; Deng, Cheng‐Hua; Gascón-Pérez, Victoria; Lusi, Matteo; Wu, Hui; Zhou, Wei; Zaworotko, Michael J.

doi:10.1021/jacs.0c01314

Cited by 67 publications

(48 citation statements)

References 63 publications

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“…Therefore combined structural and sorption studies of 1Mn show that initial chemisorption of four water molecules opens the channels in its structure, which only then enables physisorption of the remaining water. Although similar water-induced gate-opening behavior was previously reported for JUK-8, 86 SIFSIX-23-Cu 87 and the MIL-53 family, [88][89][90] to the best of our knowledge 1Mn constitutes the first case among non-reticular materials. 1Mn•8H2O shows marvelous stability during dehydration-rehydration cycling taking into account the accompanying huge unit cell volume variations.…”

Section: Resultssupporting

confidence: 84%

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

Magott¹,

Gaweł²,

Sarewicz³

et al. 2021

Preprint

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We report a non-MOF crystalline material {[Mn(imH)]2[Mo(CN)8]}n (imH = imidazole) with exceptional water sorption properties and a very large breathing effect accompanied by an outstanding stability and cyclability – properties that are absolutely unique for this class of compounds (Prussian Blue Analogs). Some previously published PBAs indeed show some sorption properties, but their cyclability is extremely limited - usually 1-3 cycles - followed by significant decomposition/amorphization. Our compound can be cycled more than 50 times without any fatigue and the sorption/desorption proceeds through four different crystal phases, which we have fully characterized structurally enabling the complete understanding of the sorption and breathing mechanism in this material - an achievement rarely reported for MOFs or PBAs. <br>The unique structure of {[Mn(imH)]2[Mo(CN)8]}n enables very strong coupling of its exceptional water sorption performance with the magnetic and photomagnetic properties of the framework, e.g. the sorption process can be followed by in-situ EPR spectroscopy with huge changes in the EPR signal intensity depending on the hydration level.<br><br>

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Section: Resultssupporting

confidence: 84%

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

Magott¹,

Gaweł²,

Sarewicz³

et al. 2021

Preprint

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“…The reaction of 1,4‐di(1 H ‐imidazol‐1‐yl)benzene ( L1 ) in DMF and Cu(SiF 6 )⋅6 H 2 O in H 2 O at room temperature afforded the purple crystals of [Cu( L1 ) 2 SiF 6 )]⋅x Solvent (NTU‐65) [16] . Single crystal X‐ray measurements reveal that NTU‐65 crystallizes in a monoclinic space group.…”

Section: Resultsmentioning

confidence: 99%

Tuning Gate‐Opening of a Flexible Metal–Organic Framework for Ternary Gas Sieving Separation

et al. 2020

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In comparison with the fast development of binary mixture separations, ternary mixture separations are significantly more difficult and have rarely been realized by a single material. Herein, a new strategy of tuning the gate‐opening pressure of flexible MOFs is developed to tackle such a challenge. As demonstrated by a flexible framework NTU‐65, the gate‐opening pressure of ethylene (C2H4), acetylene (C2H2), and carbon dioxide (CO2) can be regulated by temperature. Therefore, efficient sieving separation of this ternary mixture was realized. Under optimized temperature, NTU‐65 adsorbed a large amount of C2H2 and CO2 through gate‐opening and only negligible amount of C2H4. Breakthrough experiments demonstrated that this material can simultaneously capture C2H2 and CO2, yielding polymer‐grade (>99.99 %) C2H4 from single breakthrough separation.

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“…Flexible porous coordination polymers (PCP) are characterized by reversible structural transitions that originate from a global lattice change triggered by guest uptake and release [1–7] . This reversible structural transformation, which is termed gate‐opening behavior, occurs at a certain threshold pressure (a gate‐opening pressure) [8–18] . This feature can endow flexible PCPs with an exclusive molecular discrimination capability, which thus makes them of interest as separation media [19–25] .…”

Section: Figurementioning

confidence: 99%

Crystal Flexibility Design through Local and Global Motility Cooperation

et al. 2021

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Incorporating local mobility into a flexible framework promises to create cooperative properties unattainable in a conventional soft porous crystal. In this study, we propose a design strategy that integrates substituent moieties and a flexible porous crystal framework via intra‐framework π–π interactions. This integration not only facilitates framework structural transitions but also gives the porous coordination polymers (PCPs) different guest‐free structures that depend on the activation conditions. The incorporated flexibility gives the material the ability to discriminate C6 alkane isomers based on different gate‐opening behaviors. Thus, the PCP has potential applications in C6 isomer separation, a critical step in the petroleum refining process to produce gasoline with high octane rating. This strategy, based on ligand designability, offers a new approach to flexible PCP structural and functional design.

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Reversible Switching between Nonporous and Porous Phases of a New SIFSIX Coordination Network Induced by a Flexible Linker Ligand

Cited by 67 publications

References 63 publications

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

Large Breathing Effect Induced by Water Sorption in the Exceptionally Stable Nonporous Non-MOF Crystalline Material

Tuning Gate‐Opening of a Flexible Metal–Organic Framework for Ternary Gas Sieving Separation

Crystal Flexibility Design through Local and Global Motility Cooperation

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