Organic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks

Shen, Dengke; Cooper, James A.; Guo, Qing‐Hui; Cai, Kang; Wang, Xingjie; Wu, Huang; Chen, Hongliang; Zhang, Long; Jiao, Yang; Qiu, Yan; Stern, Charlotte L.; Liu, Zhichang; Sue, Andrew C.‐H.; Yang, Ying‐Wei; Alsubaie, Fehaid; Farha, Omar K.

doi:10.1021/jacs.9b12527

Cited by 34 publications

(20 citation statements)

References 51 publications

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“…In particular, AlOC-26-NC to AlOC-29-NC packs in a cubic manner (Figures c,d and S23–S27). It highly resembles the solid state cages produced by Stoddart and co-workers using cyclodextrin-based MOFs (CD-MOF) . Every six Al 8 rings occupy six faces of the cube, making a perfect (Al 8 ) 6 nanocage.…”

Section: Results and Discussionmentioning

confidence: 71%

Mesoporous Assembly of Aluminum Molecular Rings for Iodine Capture

et al. 2021

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The effective capture and storage of radioiodine are of worldwide interest for sustainable nuclear energy. However, the direct observation of ambiguous binding sites that accommodate iodine is extremely rare. We presented herein a crystallographic visualization of the binding of iodine within mesoporous cages assembled from aluminum molecular rings. These nanocages are formed through π−π interactions between adjacent aluminum molecular rings. Compared with the general nanotubes arrangement, the supramolecular nanocage isomer exhibits better iodine adsorption behavior. The robust molecular nanocages demonstrate a high iodine vapor saturation uptake capacity of 50.3 wt % at 80 °C. Furthermore, the resulting adsorbent can be recycled. Singlecrystal X-ray diffraction reveals binding sites of molecular I 2 within the pores of the phenyl-based linkers stabilized by the strong I•••π interactions. These compounds represent an excellent model to deduce the trapping mechanism of guest molecules interacting with the host. In addition, this work develops a promising cluster-based aluminum material as iodine adsorbents.

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Section: Results and Discussionmentioning

confidence: 71%

Mesoporous Assembly of Aluminum Molecular Rings for Iodine Capture

et al. 2021

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“…Chem. Soc.202014220422050 . γ-CD-containing hybrid metal–organic frameworks prepared by a modified vapor diffusion method, where potassium 4-methoxysalicylate is used instead of potassium hydroxide.…”

Section: Key Referencesmentioning

confidence: 99%

Cyclodextrin Metal–Organic Frameworks and Their Applications

2021

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Metrics & MoreArticle Recommendations CONSPECTUS: Cyclodextrin-based metal−organic frameworks (CD-MOFs), derived from γ-cyclodextrin (γ-CD) and alkali metal cations, constitute a class of porous, renewable, and edible MOFs that can be synthesized from a naturally occurring carbohydrate on a large scale. γ-CD is a C 8 -symmetrical cyclic oligosaccharide composed of eight asymmetric α-1,4-linked D-glucopyranosyl residues that possesses a bucket-shaped cavity with an inner diameter of ∼1 nm and a depth of ∼0.8 nm. Upon combination of 1 equiv of γ-CD with 8 equiv of potassium hydroxide in an aqueous solution, followed by vapor diffusion of MeOH (or EtOH) into this solution during several days, CD-MOF-1 is obtained as cubic crystals. This carbohydrate-based MOF, which was discovered serendipitously in 2010, was the first highly crystalline CD-MOF to be obtained. X-ray crystallography of a single crystal reveals that it adopts the space group I432 with unit cell dimensions of approximately 31 × 31 × 31 Å 3 . Other CD-MOFs, namely, CD-MOF-2 and CD-MOF-3, can be obtained when potassium ions are replaced by rubidium and cesium ions, respectively. CD-MOFs comprise extended body-centered frameworks of (γ-CD) 6 cubic units, which contain spherical pores that reside at the center of the cubes, interconnected by alkali metal cations, forming both cylindrical and triangular channels.During the past decade, CD-MOFs have emerged as a useful class of multifunctional materials based on porous frameworks with extended structures displaying robust crystallinity, permanent porosity, and excellent biocompatibility. The family of CD-MOFs has been joined by a growing collection of metal nodes involving alkali metal cations (Li + , Na + , K + , Rb + , Cs + ) and γ-CD as well as its derivatives. As a result of the ability of their extended porous frameworks to absorb guest molecules, including gases, drugs, metalbased nanoclusters, and nanoparticles, CD-MOFs have potential applications in areas as disparate as templating syntheses of metalbased nanoparticles and gels, adsorption and separation, trapping highly reactive intermediates, catalyst supports, sensing, electrical memory, and drug delivery.In this Account, we tell the story of CD-MOFs, a scientific discovery made in our research laboratory at Northwestern University, and the opportunities to use these environmentally friendly porous materials across different fields of science and technology. The story includes representative synthetic protocols for the preparation of CD-MOFs, along with an overview of their structural features, functionalization, and chemical modification aimed at increasing their stabilities in aqueous environments, and finally, a summary of their applications. The examples we will discuss, however, are only illustrative, and there is a significant body of additional findings emanating from our laboratory and others, especially in the realm of developing new synthetic strategies, tuning the framework stabilities, and exploring the guest inclusion and emergent pro...

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“…The most common and important kinds of these architectures were ones constructed by the coordination-driven self-assembly, which possess the highly directional and predictable feature to attain the desirable structure with precise shapes and sizes. A great amount of excellent work, including tetrahedra, − cubes, , octahedra, cuboctahedra, − dodecahedra, and others, ,− has been well demonstrated by Stoddart, Stang, Fujita, Leigh, Nitschke, Newkome, and many others.…”

Section: Introductionmentioning

confidence: 99%

Giant Truncated Metallo-Tetrahedron with Unexpected Supramolecular Aggregation Induced Emission Enhancement

Liu

Chen

et al. 2020

J. Am. Chem. Soc.

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The artificial synthesis of giant, three-dimensional, and shell-like architectures with growing complexity and novel functionalities is an especially challenging task for chemists. Fullerenes and self-assembled cages are remarkable examples that are proven milestones in the field of functional materials. Herein, we present another unique system: a giant terpyridine-based truncated metallo-tetrahedral architecture that includes denselypacked ionic pairs with a significant internal cavity. This huge metallo-tetrahedron with a molecular weight up to 70 000 Da was self-assembled simultaneously with 64 components: 12 large antler-shaped ligands (5), 4 star-shaped ligands (6), and 48 Cd 2+ ions. Surprisingly, the giant tetrahedron shows broad visible emission (400−640 nm) and aggregation induced emission enhancement (AIEE) via a hierarchical assembly into highly-ordered nanoaggregates. A tunable emission color and near white-light emission in mixed solvent systems were also achieved. The present work not only affords an effective approach to the creation of giant shell-like architectures that can be used to mimic biological viruses and chemical frameworks but also provides a new class of functional metallo-architectures.

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Organic Counteranion Co-assembly Strategy for the Formation of γ-Cyclodextrin-Containing Hybrid Frameworks

Cited by 34 publications

References 51 publications

Mesoporous Assembly of Aluminum Molecular Rings for Iodine Capture

Mesoporous Assembly of Aluminum Molecular Rings for Iodine Capture

Cyclodextrin Metal–Organic Frameworks and Their Applications

Giant Truncated Metallo-Tetrahedron with Unexpected Supramolecular Aggregation Induced Emission Enhancement

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