Make room for iodine: systematic pore tuning of multivariate metal–organic frameworks for the catalytic oxidation of hydroquinones using hypervalent iodine

Tahmouresilerd, Babak; Larson, Patrick; Unruh, Daniel K.; Cozzolino, Anthony F.

doi:10.1039/c8cy00794b

Cited by 21 publications

(10 citation statements)

References 49 publications

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“…For UiO‐66‐SO 3 H, the acid strength of the sulfonic acid group is stronger than that of UiO‐66‐2COOH, as evidenced by the appearance of the down‐field signal at 14.7 ppm, consistent with the result derived by using 2‐ 13 C‐acetone as the probe molecule. According to our experimental (both 13 C NMR of 2‐ 13 C‐acetone and 1 H NMR of pyridine‐d 5 ) observations, it is clear that even though the acid density in the MTV‐UiO‐66‐X catalysts is varied via altering the relative ratio, their acid strength remained almost unchanged compared with the single component having strong acid sites.…”

Section: Resultsmentioning

confidence: 78%

“…[19] Multivariate MOFs (MTV-MOFs) can serve as homogeneous and heterogeneous catalysts in asymmetric catalysts for sequential reaction of alkene epoxidation/epoxide ring-opening, [25] transformation of CO 2 into cyclic carbonates reaction, [26] and photocatalytic C-N and C-C oxidative coupling reactions. [27] Although the variation of relative ratio among different components could efficiently modify the acid density of multivariate MOFs, [28,29] the influence on the acid strength of these types of solid acid catalysts is still poorly understood.…”

Section: Introductionmentioning

confidence: 99%

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Solid‐state NMR studies of the acidity of functionalized metal–organic framework UiO‐66 materials

Tang

Xiao

et al. 2019

Magnetic Reson in Chemistry

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The acid strength of metal-organic frameworks plays a key role in their catalytic performance such as activity and selectivity during catalytic reactions. Solid-state nuclear magnetic resonance in combination with probe molecules including 2-13 C-acetone and pyridine-d 5 was employed to characterize the acid strength of UiO-66-X (X =-H,-2COOH,-SO 3 H). It was found that after introduction of the functional groups, the acid strength of UiO-66-2COOH and UiO-66-SO 3 H is considerably enhanced compared with that of parent UiO-66, with that of the former being similar to that of zeolite H-ZSM-5, and with that of the latter being slightly stronger than that of the former. Even though the acid density can efficiently be modified through changing the relative ratio in multivariate functionalized UiO-66-X, no significant alternation for the acid strength could be discerned in the MTV-UiO-66-X compared with acidic same-link counterpart. Theoretical calculations were employed to further confirm the acid strength of UiO-66-SO 3 H and UiO-66-2COOH.

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Section: Resultsmentioning

confidence: 78%

Section: Introductionmentioning

confidence: 99%

Solid‐state NMR studies of the acidity of functionalized metal–organic framework UiO‐66 materials

Tang

Xiao

et al. 2019

Magnetic Reson in Chemistry

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“…Catalyst 266 can be readily recycled with high catalytic efficiency, whereas a sharp decrease occurs in the catalytic activity of 267 due to aggregation of catalyst particles during the reaction. 121…”

Section: Metal–organic-framework (Mof)-hybridized Hypervalent Iodine ...mentioning

confidence: 99%

“…Highly stable MOF multivariate MIL-53 (Al) and UiO-66 (Zr) supporting varying percentages of linker have been developed by Cozzolino and co-workers. 121 UiO-66 25%-I (266) is reportedly more efficient than MIL-53 25%-I (267) toward the oxidation of hydroquinone (265) (Scheme 50). Catalyst Cardenal and co-workers investigated the coordination chemistry of iodosylbenzenes with transition-metal clusters, such as carboxylate-bridged Zn 2 complexes and Zr 6 O 4 clusters, commonly encountered in MOFs.…”

Section: Metal-organic-framework (Mof)-hybridized Hypervalent Iodine ...mentioning

confidence: 99%

Recyclable Hypervalent Iodine Reagents in Modern Organic Synthesis

et al. 2022

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Hypervalent iodine (HVI) reagents have gained much attention as versatile oxidants because of their low toxicity, mild reactivity, easy handling, and availability. Despite their unique reactivity and other advantageous properties, stoichiometric HVI reagents are associated with the disadvantage of generating non-recyclable iodoarenes as waste/co-products. To overcome these drawbacks, the syntheses and utilization of various recyclable hypervalent iodine reagents have been established in recent years. This review summarizes the development of various recyclable non-polymeric, polymer-supported, ionic-liquid-supported, and metal–organic framework (MOF)-hybridized HVI reagents.1 Introduction2 Polymer-Supported Hypervalent Iodine Reagents2.1 Polymer-Supported Hypervalent Iodine(III) Reagents2.2 Polymer-Supported Hypervalent Iodine(V) Reagents3 Non-Polymeric Recyclable Hypervalent Iodine Reagents3.1 Non-Polymeric Recyclable Hypervalent Iodine(III) Reagents3.2 Recyclable Non-Polymeric Hypervalent Iodine(V) Reagents3.3 Fluorous Hypervalent Iodine Reagents4 Ionic-Liquid/Ion-Supported Hypervalent Iodine Reagents5 Metal–Organic Framework (MOF)-Hybridized Hypervalent Iodine Reagents6 Conclusion

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“…MOFs possess unique property among the various microporous and mesoporous materials, creating interest for an unprecedented range of applications 2 . As a new class of crystalline nanoporous materials, MOFs have been found extensively applied in the areas such as catalysis 3 , biomedicine 4 , separation 5 , gas storage 6 , chemical sensing 7 , air purification 8 , imaging agents 9 , and so on.…”

mentioning

confidence: 99%

Computational characterization of halogen vapor attachment, diffusion and desorption processes in zeolitic imidazolate framework-8

Han

et al. 2020

Sci Rep

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Computational simulation methods are used for characterizing the detailed attachment, diffusion and desorption of halogen vapor molecules in zeolitic imidazolate framework-8 (ZIF-8). The attachment energies of Cl 2 , Br 2 and i 2 are −55.2, −48.5 and −43.0 kJ mol −1 , respectively. The framework of ZIF-8 is disrupted by Cl 2 , which bonds with Zn either on the surface or by freely diffusing into the cage. A framework deformation on the surface of ZIF-8 can be caused by the attachment of Br 2 , but only reorientation of the 2-methylimidazolate linkers (mIms) for I 2. In diffusion, the halogen molecules have a tendency to vertically permeate the apertures of cages followed with swing effect implemented by the mIms. Larger rotation angles of mIms are caused by Br 2 because of its stronger interaction with mIms than i 2. A maximum of 7 Br 2 or 5 I 2 molecules can be accommodated in one cage. Br 2 are clinging to the mIms and I 2 are arranged as crystal layout in the cages, therefore in desorption processes molecules attached to the surface and free inside are desorbed while some remained. These results are beneficial for better understanding the adsorption and desorption processes of halogen vapors in the porous materials.

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Make room for iodine: systematic pore tuning of multivariate metal–organic frameworks for the catalytic oxidation of hydroquinones using hypervalent iodine

Abstract: A multivariate approach has been to to establish the right balance between iodine loading and pore size for catalytic oxidative dearomatizations in MIL-53 (Al) and UiO-66 (Zr) MOFs.

Cited by 21 publications

References 49 publications

Solid‐state NMR studies of the acidity of functionalized metal–organic framework UiO‐66 materials

Solid‐state NMR studies of the acidity of functionalized metal–organic framework UiO‐66 materials

Recyclable Hypervalent Iodine Reagents in Modern Organic Synthesis

Computational characterization of halogen vapor attachment, diffusion and desorption processes in zeolitic imidazolate framework-8

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