Fluorinated leaning pillar[6]arene: synthesis, structure and selective iodide anion binding by anion–π interactions

Li, Weichun; Qin, Peng; Zhao, Xingxing; Qu, Wenjuan; Lin, Qi; Yao, Hong; Wei, Tai‐Bao; Zhang, You‐Ming; Liu, Yuezhou; Shi, Bingbing

doi:10.1039/d2ob01579j

“…From a design perspective, improving hydrophobicity of the sieving platform can improve the kinetics of hydrocarbon separation. This has been verified in organic cages and MOFs where using fluorine improved not only hydrophobicity but also thermal stability [37–45] . Herein, an adaptive porous fluorinated leaning pillararene was synthesized with persistent porosity and was efficiently employed to separate benzene traces after catalytic hydrogenation to produce high purity cyclohexane under dynamic conditions (Figure 1).…”

Section: Figurementioning

confidence: 78%

Fluorine‐Boosted Kinetic and Selective Molecular Sieving of C6 Derivatives

Moosa,

Alimi,

Lin

et al. 2023

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Porous molecular sorbents have excellent selectivity towards hydrocarbon separation with energy saving techniques. However, to realize commercialization, molecular sieving processes should be faster and more efficient compared to extended frameworks. In this work, we show that utilizing fluorine to improve the hydrophobic profile of leaning pillararenes affords a substantial kinetic selective adsorption of benzene over cyclohexane (20:1 for benzene). The crystal structure shows a porous macrocycle that acts as a perfect match for benzene in both the intrinsic and extrinsic cavities with strong interactions in the solid state. The fluorinated leaning pillararene surpasses all reported organic molecular sieves and is comparable to the extended metal organic frameworks that were previously employed for this separation such as UIO‐66. Most importantly, this sieving system outperformed the well‐known zeolitic imidazolate frameworks under low pressure, which opens the door to new generations of molecular sieves that can compete with extended frameworks for more sustainable hydrocarbon separation.

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“…Fluorinated leaning pillar[6]arene FP6 and its single crystal structure (CCDC 2024931) were obtained as described previously [44] . Moreover, we further investigated the yield of the reaction under different conditions (Table S1).…”

Section: Methodsmentioning

confidence: 99%

“…Fluorinated leaning pillar [6]arene FP6 and its single crystal structure (CCDC 2024931) were obtained as described previously. [44] Moreover, we further investigated the yield of the reaction under different conditions (Table S1). Taking advantage of the fragment cyclization method, macrocyclic condensation reaction was examined under various reaction conditions.…”

Section: Methodsmentioning

confidence: 99%

“…[27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43] Recently, our group reported a novel electron-deficient fluorinated leaning pillar [6]arene (FP6) which contains two tetrafluorobenzene units (Figure 1, Table S1). [44] In the crystal structure of FP6, two tetrafluorobenzene groups on the macrocycle tilted to the same direction, leading to a leaning structure of FP6 in the solid state. [44] The distance between two tetrafluorobenzene groups is calculated to be 9.65 Å.…”

Section: Introductionmentioning

confidence: 99%

“…[44] In the crystal structure of FP6, two tetrafluorobenzene groups on the macrocycle tilted to the same direction, leading to a leaning structure of FP6 in the solid state. [44] The distance between two tetrafluorobenzene groups is calculated to be 9.65 Å. And the two farthest carbon atoms on the methylene bridges is Here, we report that an easily obtained fluorinated leaning pillar [6]arene (FP6) was employed as an efficient adsorbent for iodine capture.…”

Section: Introductionmentioning

confidence: 99%

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Capture and Removal of Iodine by a Fluorinated Leaning Pillar[6]arene with Host–Guest Interactions

Shi

¹

,

Li

²

,

Qin

³

et al. 2023

ChemNanoMat

Self Cite

2

0

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Volatile radioactive pollutants are posing great challenges to global environment. Volatile radioactive iodine, which is one of the primary environmental pollutants from nuclear power plants, spreads rapidly in water and air and increases risk to human health. Therefore, the research for appropriate adsorbents to capture iodine with long-term storage is crucial. In this study, we report that easily obtained fluorinated leaning pillar[6]arene FP6 is a new adsorbent for iodine capture with robust moisture and thermal stability. Crystalline solid FP6 solid can capture not only volatile iodine in the air but also iodine dissolved in aqueous solutions with fast adsorption speed and high up-take capacity. Host-guest interactions between FP6 and iodine indicates that iodine molecule is threaded into the cavity of the cyclic host FP6 to form a host-guest complex driven by CÀ F ••• I halogen bonding interactions. Moreover, the regeneration of FP6 is simple and efficient, and it can be regenerated at least five times by simply heating under vacuum at 120 °C for 3 hours without losing iodine capture capacity. The excellent iodine pollutant removal ability demonstrates the promise of FP6 for pollutant treatment.

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Fluorine‐Boosted Kinetic and Selective Molecular Sieving of C6 Derivatives

Moosa,

Alimi,

Lin

et al. 2023

Angewandte Chemie

0

View full text Add to dashboard Cite

Porous molecular sorbents have excellent selectivity towards hydrocarbon separation with energy saving techniques. However, to realize commercialization, molecular sieving processes should be faster and more efficient compared to extended frameworks. In this work, we show that utilizing fluorine to improve the hydrophobic profile of leaning pillararenes affords a substantial kinetic selective adsorption of benzene over cyclohexane (20:1 for benzene). The crystal structure shows a porous macrocycle that acts as a perfect match for benzene in both the intrinsic and extrinsic cavities with strong interactions in the solid state. The fluorinated leaning pillararene surpasses all reported organic molecular sieves and is comparable to the extended metal organic frameworks that were previously employed for this separation such as UIO‐66. Most importantly, this sieving system outperformed the well‐known zeolitic imidazolate frameworks under low pressure, which opens the door to new generations of molecular sieves that can compete with extended frameworks for more sustainable hydrocarbon separation.

show abstract

Fluorinated leaning pillar[6]arene: synthesis, structure and selective iodide anion binding by anion–π interactions

Abstract: Anion recognition has continuously attracted significant attention due to its important role in environmental and biological scienc-es. Here, we designed and synthesized an electron-deficient fluorinated leaning pillar[6]arene 1 which contained...

Cited by 9 publications

References 60 publications

Fluorine‐Boosted Kinetic and Selective Molecular Sieving of C6 Derivatives

Fluorine‐Boosted Kinetic and Selective Molecular Sieving of C6 Derivatives

Capture and Removal of Iodine by a Fluorinated Leaning Pillar[6]arene with Host–Guest Interactions

Fluorine‐Boosted Kinetic and Selective Molecular Sieving of C6 Derivatives

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