Oxidation State Distributions Provide Insight into Parameters Directing the Assembly of Metal–Organic Nanocapsules

Rathnayake, Asanka S.; Fraser, Hector W. L.; Brechin, Euan K.; Dalgarno, Scott J.; Baumeister, Jakob E.; Rungthanaphatsophon, Pokpong; Walensky, Justin R.; Barnes, Charles L.; Atwood, Jerry L.

doi:10.1021/jacs.8b07775

Cited by 11 publications

(18 citation statements)

References 55 publications

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“…[11][12][13][14][15][16][17][18][19][20] Crystalline CAMs with large pores drew extraordinary attention owing to their promising guest-molecule encapsulation capacities, which demonstrate broad application prospect in chemical sensing, catalysis, drug delivery, and host-guest chemistry. [21][22][23][24][25][26] Although many research endeavors have focused on the development of new crystalline CAMs, it is unfortunate that those with large pores, high-porosity, and noninterpenetrated structures have rarely been reported, probably because constructing novel porous crystalline CAMs still present an enduring and significant challenge. Thus further detailed exploration of their properties and applications remains poorly understood.…”

Section: Introductionmentioning

confidence: 99%

Mesoporous Crystalline Silver-Chalcogenolate Cluster-Assembled Material with Tailored Photoluminescence Properties

Wang

Yan

et al. 2019

CCS Chem

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Crystalline cluster-assembled materials (CAMs) are emerging as types of exploratory fabrications due to their atomically precise structures and intriguing chemical/physical properties, as well as their luminescent function. However, constructing novel luminescent porous crystalline CAMs present an enduring and significant challenge owing to their instability and poor ambient-temperature photoluminescent quantum yields. In this work, we synthesized successfully, a mesoporous crystalline CAM (1 ⊃ DMAC), based on silver-chalcogenolate cluster and 1,1,2,2-tetrakis(4-(pyridin-4-yl)phenyl)ethene (TPPE) ligand, with highsymmetry structure and ultralarge pores. 1 ⊃ DMAC exhibited adjustable intense luminescence, originating from aggregation-induced emission (AIE) properties of the TPPE ligand. The diameter of the cubic cage in 1 ⊃ DMAC was as high as 32 Å, which endowed it with satisfactory encapsulation capacity for different guest molecules. Interestingly, by adjusting functionalized guest molecules, circularly polarized luminescence, white-light-emitting, and room-temperature phosphorescence were readily realized. 1 ⊃ DMAC could enrich limited kinds of mesoporous crystalline CAMs and offers the prospect of application in host-guest chemistry. More importantly, this work provides a strategy, versatile for tailoring luminescence in crystalline porous materials.

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Section: Introductionmentioning

confidence: 99%

Mesoporous Crystalline Silver-Chalcogenolate Cluster-Assembled Material with Tailored Photoluminescence Properties

Wang

Yan

et al. 2019

CCS Chem

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“…MONCs seamed by redox stable metal ions (for example, Zn II , Mg II , or Ga III ), are relatively easy to synthesize, while those constructed from redox-active metals are relatively difficult. [31][32][33]62 Previous works have demonstrated that the reaction of Mn II or Fe II with pyrogallol [4]arenes yields MONCs with metal ions in mixed valence. 31−33 The complicated coordination environment is not favorable to form CP-MONCs.…”

Section: Coordination Polymers Based On Hexameric Moncsmentioning

confidence: 99%

“…Metal–organic nanocapsules (MONCs) are self-assembled capsule-like nanostructures with permanent internal cavities and fantastic geometrical shapes. − In particular, MONCs constructed with metal ions and bowl-shaped C- alkylpyrogallol[4]arenes (PgCs) have attracted great attention because of their unique and robust structures. − ,− Twelve phenolic hydroxy groups on the upper rim of the PgC seam with appropriate metal ions result in the formation of hierarchical superstructures. To date, studies on PgC-assembled MONCs have been focused on the synthesis of capsules by employing various metal ions or control of the internal volume of the MONCs (i.e., dimeric and hexameric capsules). ,,− Recently, a new discovery related to the modification of the exoligand on the surface of the MONCs is of great interest to us: these MONCs possess a large number of open metal sites on their exterior, making it facile to assemble MONCs into hierarchical coordination polymers. ,, Coordination polymers constructed from PgC-assembled MONCs (CP-MONCs) can be considered as another type of metal–organic framework (MOF) with higher complexity (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Coordination Polymers Constructed from Pyrogallol[4]arene-Assembled Metal–Organic Nanocapsules

Shao

Sikligar

et al. 2021

Acc. Chem. Res.

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Conspectus Coordination polymers, commonly known as infinite crystalline lattices, are versatile networks and have diverse potential applications in the fields of gas storage, molecular separation, catalysis, optics, and drug delivery, among other areas. Secondary building blocks, mainly incorporating rigid polydentate organic linkers and metal ions or clusters, are commonly employed to construct coordination polymers. Recently, novel building blocks such as coordination polyhedra have been utilized as metal nodes to fabricate coordination polymers. Benefiting from the rigid porous structure of the coordination polyhedron, prefabricated designer “pores” can be incorporated in this type of coordinate polymer. In this Account, coordination polymers built by pyrogallol[4]arene-assembled metal–organic nanocapsules are summarized. This class of metal–organic nanocapsule possesses the following advantages that make them excellent candidates in the construction of coordination polymers: (i) Various geometrical shapes with different volumes of the inner cavities can be obtained from these capsules. Among them, the two main categories illustrated are dimeric and hexameric capsules, which comprise two and six pyrogallol[4]arenes units, respectively. (ii) A wide range of possible metal ions ranging from main group metals to transition metals and even lanthanides have been demonstrated to seam the capsules. Therefore, these coordination polymers can be endowed with fascinating functionalities such as magnetism, semiconductivity, luminescence, and radioactivity. (iii) Up to 24 metal ions have been successfully embedded on the surface of the nanocapsule, each a potential reaction site in the construction of coordination polymers, opening up pathways for the formation of multidimensional frameworks. In this Account, we focus primarily on the synthesis and the structural information on pyrogallol[4]arene-derived coordination polymers. Coordination polymers can be formed by introducing linkers with two coordination sites, using pyrogallol[4]arenes with coordination sites on the tail, or even via metal ions cross-linking with each other. Machine learning was recently developed to help us predict and screen the structures of the coordination polymers. With single crystal analysis in hand, detailed structural information provides a molecular-level perspective. Significantly, following the formation of coordination polymers, the overall shape and structure of the discrete metal–organic nanocapsules remains essentially unchanged, with full retention of the prefabricated pores. If a rigid linker is used to connect capsules, more than one lattice void with different volumes can be found within the framework. Thus, molecules with different sizes could potentially be encapsulated within these coordination polymers. In addition, flexible ligands can also be employed as linkers. For example, polymers have been employed as large linkers that transform the crystalline coordination polymers into polymer matrices, paving the way toward the ...

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“…The cone-shaped PgCn, which is the tetramer of the natural phenolic mimic pyrogallol (PG) with variable length sidechain groups (Figure 1c), has been demonstrated as a versatile precursor for construction of metal-organic nanocapsules. [24][25][26][27][28][29][30][31][32][33][34] Based on coordination assemblies of PgCn (n = 3, 5 or 9) with actinides ions, we have achieved high-performance uranyl capture via uranyl-PgCn nanocages (Figure 1d) assembled in situ in monophasic or biphasic solvent systems. This type of extraction as nanoscale species is unprecedented for actinide ions and it leads to a novel paradigm for hybrid nanocluster-based actinide sequestration, which may be considered as "nanoextraction".…”

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confidence: 99%

Actinide Separation Inspired by Self-Assembled Metal–Polyphenolic Nanocages

Mei

Ren

et al. 2020

J. Am. Chem. Soc.

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The separation of actinides has a vital place in nuclear fuel reprocessing, recovery of radionuclides and remediation of environmental contamination. Here we propose a new paradigm of nanocluster-based actinide separation, namely nano-extraction, that can achieve efficient sequestration of uranium in an unprecedented form of giant coordination nanocages using a cone-shaped macrocyclic pyrogallol [4]arene as the extractant. The U 24 -based hexameric pyrogallol[4]arene nanocages with distinctive [U 2 PG 2 ] binuclear units (PG = pyrogallol), that rapidly assembled in situ in monophasic solvent, were identified by single-crystal XRD, MALDI-TOF-MS, NMR, and SAXS/SANS. Comprehensive biphasic extraction studies show that this novel separation strategy has enticing advantages such as fast kinetics, high efficiency, and good selectivity over lanthanides, and thus demonstrate its potential for efficient separation of actinide ions.

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Oxidation State Distributions Provide Insight into Parameters Directing the Assembly of Metal–Organic Nanocapsules

Cited by 11 publications

References 55 publications

Mesoporous Crystalline Silver-Chalcogenolate Cluster-Assembled Material with Tailored Photoluminescence Properties

Mesoporous Crystalline Silver-Chalcogenolate Cluster-Assembled Material with Tailored Photoluminescence Properties

Coordination Polymers Constructed from Pyrogallol[4]arene-Assembled Metal–Organic Nanocapsules

Actinide Separation Inspired by Self-Assembled Metal–Polyphenolic Nanocages

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