Precise Assembly and Supramolecular Catalysis of Tetragonal- and Trigonal-Elongated Octahedral Coordination Containers

Sheng, Tianlu; He, Chang; Wang, Zhenqiang; Zheng, Ganhong; Dai, Fulong; Chen, Xiaoming

doi:10.31635/ccschem.021.202100987

Cited by 14 publications

(9 citation statements)

References 46 publications

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“…However, reaction of 2,7,9-triphenylcarbazole-3,6-dicarboxylic acid (H 2 tpcd) with MgCl 2 ·6H 2 O, MnCl 2 ·4H 2 O, Co(NO 3 ) 2 ·6H 2 O, or Ni(NO 3 )·6H 2 O and p-tert -butylsulfonylcalix[4]arene in amide/alcohol mixtures affords the targeted [(M 4 X(SC4A)) 2 (tpcd) 4 ] 2− (M = Mg 2+ , Mn 2+ , Co 2+ , and Ni 2+ ; X = OH − or OMe − ; hereafter referred to as M-TriPhenyl-cdc) cages in high yield. While the μ 4 species present in the metal cation clusters that comprise these cages can vary 2,23,30 the cages isolated here feature either methoxide or hydroxide ions in these positions. As a result, the cages present as 2 − anions.…”

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Controlling phase in low-nuclearity calixarene-capped porous coordination cages with ligand functionalization

et al. 2022

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confidence: 89%

Controlling phase in low-nuclearity calixarene-capped porous coordination cages with ligand functionalization

et al. 2022

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“…Coordination containers, also known as metal–organic polyhedra, are one of the most fascinating classes of synthetic receptors formed via coordination-driven self-assembly. Their applications in guest encapsulation and recognition, − catalysis, − and biomedical settings − have been widely investigated. Taking advantage of both the intrinsic and extrinsic porosity ,,− of coordination containers, they have been demonstrated to be excellent candidates for the storage and separation of small molecules .…”

Section: Introductionmentioning

confidence: 99%

Iodine Adsorption via Porous Molecular Solids Based on Coordination Containers Derived from Naphthalene-1,8-dicarboxylate

Liu

Sheng

et al. 2022

Crystal Growth & Design

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Efficient methods to sequester the radioactive iodine element are urgently needed in the nuclear and environmental industries. Nanoporous solid adsorbents based on container molecules are particularly suited for achieving iodine sequestration due to their uniquely tunable intrinsic and extrinsic porous structure. In the present work, we describe the design and synthesis of two new coordination containers based on a sulfonylcalixarene precursor and naphthalene-1,8-dicarboxylate linker and demonstrate their promising application for iodine adsorption and release. We show that, in addition to the more common C−H•••π hydrogen bonding and hydrophobic interactions, another less appreciated type of noncovalent interaction, namely, a dual Br•••π binding motif, can be introduced through the modification of the dicarboxylate linker with a bromine substituent to strengthen the crystal packing and maintain the solid-state porosity of the molecular containers. These synthetic coordination containers not only exhibit an excellent adsorption capacity for iodine vapor at a solid−gas interface but also show an effective iodine capture ability from a hexane solution through a solid−liquid interface. Importantly, the adsorption of iodine by these porous molecular solids displays remarkable reversibility and recyclability, indicating their promising practical utility for iodine capture and release.

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“…Metal–organic macrocycles and cages − have undergone extensive development over the last few decades. By virtue of the efficient coordination-driven self-assembly strategy, − many aesthetically fascinating two-dimensional (2D) and three-dimensional (3D) supramolecular architectures stemming from simple organic ligands and metal components have been reported. Most of these metal–ligand edifices are charged, and charge plays an important role in their functions, such as host–guest encapsulation, − catalysis, − etc.…”

Section: Introductionmentioning

confidence: 99%

Controlled Self-Assembly, Isomerism, and Guest Uptake/Release of Charge-Reversible Lanthanide–Organic Octahedral Cages

Zhou

Feng

et al. 2023

J. Am. Chem. Soc.

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Charge plays a crucial role in the function of molecular and supramolecular systems, but coordination hosts capable of orthogonal charge regulation remain elusive so far. In this study, we report the condition-dependent self-assembly of charge-reversible lanthanide−organic tetra-capped octahedral cages, i.e., [Ln 6 (H 3 L) 4 ] 6+ and [Ln 6 L 4 ] 6− , from a series of lanthanide ions (Ln 3+ ; Ln = Lu, Yb, Eu) and a tritopic tetradentate acylhydrazone ligand (H 6 L) featuring multiple deprotonation states and propeller conformations. While direct self-assembly under basic conditions produced a mixture of various Δ x Λ 6−x -[Ln 6 L 4 ] 6− (x = 0−6) stereoisomers, racemic Δ 6 -and Λ 6 -[Ln 6 L 4 ] 6− could be exclusively obtained from the first self-assembly of Δ 6 -and Λ 6 -[Ln 6 (H 3 L) 4 ] 6+ under neutral conditions followed by postassembly deprotonation. Rich isomerism on the tetra-capped octahedral cages arising from the coupling between the metal-centered Δ/Λ chirality and the ligand conformations has been discussed based on X-ray single-crystal structures of the C 3 -symmetric Δ 3 Λ 3 -Ln 6 L 4 and T-symmetric Δ 6 /Λ 6 -Ln 6 L 4 complexes. Host−guest studies confirmed that positively charged rac-Δ 6 /Λ 6 -[Ln 6 (H 3 L) 4 ] 6+ could bind anionic sulfonates, and negatively charged rac-Δ 6 /Λ 6 -[Ln 6 L 4 ] 6− exhibited strong encapsulation ability toward ammonium guests, where acid/base-triggered guest uptake/release could be realized taking advantage of the charge reversibility of the cage. Moreover, photophysical studies revealed visible-light-sensitized and guest-encapsulation-enhanced NIR emissions on the rac-Δ 6 / Λ 6 -Yb 6 L 4 cage. This work not only enriches the library of functional lanthanide−organic cages but also provides a promising candidate with charge reversibility for the development of smart supramolecular materials.

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Precise Assembly and Supramolecular Catalysis of Tetragonal- and Trigonal-Elongated Octahedral Coordination Containers

Cited by 14 publications

References 46 publications

Controlling phase in low-nuclearity calixarene-capped porous coordination cages with ligand functionalization

Controlling phase in low-nuclearity calixarene-capped porous coordination cages with ligand functionalization

Iodine Adsorption via Porous Molecular Solids Based on Coordination Containers Derived from Naphthalene-1,8-dicarboxylate

Controlled Self-Assembly, Isomerism, and Guest Uptake/Release of Charge-Reversible Lanthanide–Organic Octahedral Cages

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