Chemistry of Soft Porous Crystals: Structural Dynamics and Gas Adsorption Properties

Krause, Simon; Hosono, Nobuhiko; Kitagawa, Susumu

doi:10.1002/anie.202004535

Cited by 314 publications

(256 citation statements)

References 237 publications

(188 reference statements)

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“…After that, the enthalpy first reduced to 51.2 kJ mol À1 at 0.086 mmol g À1 ,m eaning that the endothermic pore-opening action occur mainly at this stage. [23] After complete pore opening, the enthalpy quickly recovered to 51.9 kJ mol À1 , corresponding to the adsorption in 1.…”

Section: Stability and Hydrophobicitymentioning

confidence: 99%

A Hydrogen‐Bonded yet Hydrophobic Porous Molecular Crystal for Molecular‐Sieving‐like Separation of Butane and Isobutane

Zhang

Liao

et al. 2020

Angewandte Chemie

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Porous molecular crystals sustained by hydrogen bonds and/or weaker connections are an intriguing type of adsorbents,b ut they rarely demonstrate efficient adsorptive separation because of poor structural robustness and tailorability.Herein, we report aporous molecular crystal based on hydrogen-bonded cyclic dinuclear Ag I complex, whichexhibits exceptional hydrophobicity with awater contact angle of 1348 8, and high chemical stability in water at pH 2-13. The seemingly rigid adsorbent shows apore-opening or nonporous-to-porous type butane adsorption isotherm and complete exclusion of isobutane,indicating potential molecular sieving. Quantitative column breakthrough experiments show slight co-adsorption of isobutane with an experimental butane/isobutane selectivity of 23, and isobutane can be purified more efficiently than for butane.I nsitu powder/single-crystal X-rayd iffraction and computational simulations reveal that at rivial guest-induced structural transformation playsac ritical role.

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Section: Stability and Hydrophobicitymentioning

confidence: 99%

A Hydrogen‐Bonded yet Hydrophobic Porous Molecular Crystal for Molecular‐Sieving‐like Separation of Butane and Isobutane

Zhang

Liao

et al. 2020

Angewandte Chemie

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“…Incorporation of local dynamics into flexible frameworks is a promising method for creating cooperative flexibility that is unattainable in conventional PCPs [30] . Efforts to this end have been attempted by introducing dynamic sidearms into the pillar of flexible PCPs; [31–33] however, novel cooperative properties, other than an altered gate‐opening pressure, have not been demonstrated.…”

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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“…These so-called so porous crystals (SPCs) 14 or exible MOFs 15 exhibit strong deformation of the lattice in particular upon adsorption or desorption of guest species. 16 Such guest-induced transitions are specic to nanoscopic metamaterials, as they rely on enhanced host-guest interactions due to connement at the molecular scale. As a consequence, SPCs can exhibit exotic adsorption properties with application in the area of gas storage, separation and sensing.…”

Section: Introductionmentioning

confidence: 99%