Hierarchical Coordination Frameworks Based on Metal–Organic Dimeric Nanocapsules Comprising Praseodymium and Pyrogallol[4]arene

Sikligar, Kanishka; Kelley, Steven P.; Shao, Li; Baker, Gary A.; Atwood, Jerry L.

doi:10.1021/acs.cgd.0c01482

Cited by 8 publications

(9 citation statements)

References 54 publications

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“…To date, several hierarchical architectures have been created by the coordination-driven self-assembly of SBBs (Perry IV et al, 2009;Chen et al, 2015;Nouar et al, 2008). These SBBs are mostly assembled into one-dimensional polymers (Yoo et al, 2015;Mai et al, 2018;Hong et al, 2000;Li et al, 2011;Liu et al, 2012;Sikligar et al, 2021) or metal-organic frameworks (Pang et al, 2014;Qian et al, 2014;Li et al, 2009;Tian et al, 2014;Park et al, 2007;Nouar et al, 2008).…”

Section: Introductionmentioning

confidence: 99%

Hierarchical packing of racemic metallosupramolecular cages with Ni(II)-based triple-stranded helicate building blocks

Nguyen¹,

Nguyễn²,

Tran³

et al. 2023

Int Union Crystallogr J

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Three novel hierarchical Ni-based metallosupramolecular cages were constructed from nickel ions, pyridine dicarboxylates and isophthalate derivative ligands (the substituents on C5 of isophthalate are methyl, tert-butyl and bromo groups). In every cage, two multinuclear nickel clusters, assembled from four nickel atoms and three pyridine dicarboxylate ligands, are interlinked by three isophthalate-derivative ligands to form a nickel-based triple-stranded helicate (TSH), which then becomes the supramolecular building block for the fabrication of a metallocage. Six homochiral TSH supramolecular building blocks, either left (M)-handed or right (P)-handed, are connected by four linking nickel atoms to generate M 6 and P 6 discrete racemic cage molecules (M 6 – cage with six M-TSHs; P 6 – cage with six P-TSHs). The crystal packing of the racemic cages was characterized by single-crystal X-ray diffraction. An additional cobalt-based molecular cage with 5-methylisophthalate bridging ligands was synthesized for host–guest interaction studies. The methyl groups in Co- and Ni-TSH can act as guest units to be accommodated in the cone-shaped metal clusters (host) of an adjacent cage.

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Section: Introductionmentioning

confidence: 99%

Hierarchical packing of racemic metallosupramolecular cages with Ni(II)-based triple-stranded helicate building blocks

Nguyen¹,

Nguyễn²,

Tran³

et al. 2023

Int Union Crystallogr J

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“…Our group has been dedicated to the design and construction of CP-MONCs and has made considerable progress. − ,,,− In this Account, we will summarize the current status of CP-MONCs as prototypes in the field. Particular attention will be paid to the different topological structures derived from the various coordinate behaviors.…”

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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“…Solvothermal reactions remain a useful synthetic approach for accessing a range of nanocapsular 53,54 and hierarchical assemblies. 28 Using solvothermal methods under pressure (e.g., autoclave or pressure vessel, such as a Parr PTFE-lined digestion bomb) allows the use of low-boiling solvents to act as ligands and participate in self-assembly in ways inaccessible to many conventional (e.g., slow evaporation, slow cooling, vapor diffusion, liquid diffusion) techniques employing volatile solvents, such as acetonitrile. gallol [4]arene was shown to yield Mg-seamed polymeric poly(ethylene glycol) hexameric pyrogallol [4]arene MONC networks cross-linked by ethylene glycol or diethylene glycol units.…”

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confidence: 99%

“…Hexameric nanocapsules have been seamed together by metal ions such as Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Mg 2+ , Mn 2+ , In 3+ , Fe 2+ /Fe 3+ , V 4+ , and Ga 3+ . Homodimeric nanocapsules have been successfully constructed from a similar range of metal ions: Cu 2+ , Zn 2+ , Ni 2+ , Co 2+ , Gd 3+ , Dy 3+ , and Pr 3+ . These MONCs have been further applied as giant, rigid building blocks to generate hierarchical self-assemblies. ,− For instance, two-dimensional coordination networks were synthesized from nanocapsules seamed by the metal ions Zn 2+ , , Ni 2+ , Mg 2+ , , and Mn 2+ …”

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confidence: 99%

“…In the current study, solvothermal reactions of cesium iodide with C -alkylpyrogallol[4]arene ligands in N,N -dimethylformamide (DMF) are used to prepare coordination networks displaying pronounced Cs + cation−π interactions. Solvothermal reactions remain a useful synthetic approach for accessing a range of nanocapsular , and hierarchical assemblies . Using solvothermal methods under pressure (e.g., autoclave or pressure vessel, such as a Parr PTFE-lined digestion bomb) allows the use of low-boiling solvents to act as ligands and participate in self-assembly in ways inaccessible to many conventional (e.g., slow evaporation, slow cooling, vapor diffusion, liquid diffusion) techniques employing volatile solvents, such as acetonitrile.…”

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confidence: 99%

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Cesium Cation−π Interactions Stabilize Pyrogallol[4]arene Coordination Networks

Sikligar

Kelley

Baker

et al. 2022

Crystal Growth & Design

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Pyrogallol[4]arene macrocycles represent versatile precursors for the rational design of a rapidly expanding range of coordination networks, metal−organic nanocapsules, hierarchical nanocapsular assemblies, and elegant nanostructures. In this work, the solvothermal reaction of C-alkylpyrogallol[4]arene (alkyl = methyl, ethyl) in cesiumcontaining N,N-dimethylformamide (DMF) afforded coordination networks having a composition of [Cs 2 (C-methylpyrogallol[4]arene)(DMF)]•(DMF) 2 and [Cs 2 (C-ethylpyrogallol[4]arene)(DMF) 3 ], respectively. These extended coordination networks each display a duplicity of cesium environments featuring both (i) a "pseudocrown ether" environment involving O-coordination between Cs + and the phenolic oxygens of four neighboring doubly deprotonated C-alkylpyrogallol[4]arenes, plus DMF ligation, and (ii) polyhapto η 6 -type coordination of a Cs + center by the four phenyl rings of a C-alkylpyrogallol[4]arene receptor. The presence of both an exo coordination mode in which the cesium cation is bound to the "hard" phenolic/phenoxide upper rim pyrogallol[4]arene oxygens plus an endo one corresponding to cesium cation−π bonding by the "soft" aromatic rings defining the pyrogallol[4]arene cavity is unique among pyrogallol [4]arene chemistry. This duality is pivotal to the cross-linking arrangement which yields an extended network and suggests that a number of interesting architectures might be identified by further study of alkali metal-incorporated C-alkylpyrogallol[4]arene systems.

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Hierarchical Coordination Frameworks Based on Metal–Organic Dimeric Nanocapsules Comprising Praseodymium and Pyrogallol[4]arene

Cited by 8 publications

References 54 publications

Hierarchical packing of racemic metallosupramolecular cages with Ni(II)-based triple-stranded helicate building blocks

Hierarchical packing of racemic metallosupramolecular cages with Ni(II)-based triple-stranded helicate building blocks

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

Cesium Cation−π Interactions Stabilize Pyrogallol[4]arene Coordination Networks

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