A Thiacalix <i>Basket</i> and Its Anion‐Dependent 2‐D and 3‐D Silver(I) Coordination Polymers via Exo‐Coordination

Ju, Huiyeong; Park, In‐Hyeok; Lee, Eunji; Kim, Chungsik; Kim, Seulgi; Kuwahara, Shunsuke; Habata, Yoichi; Lee, Shim Sung

doi:10.1002/ejic.201901216

Cited by 6 publications

(4 citation statements)

References 50 publications

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“…In the core coordination unit of the 1D chain, the Ag + ion adopts a distorted tetrahedral geometry with two oxygen atoms of two linker ClO 4 ions and two sulfur atoms from the bridging unit and lower rim (Figure S5c). Similar uncommon behavior of the ClO 4 anion as a linker in the dimensional framework has been recently documented for the 2D network of the Ag complex of thiacalix [4]biscrown-ether [21]. Interestingly, thiacalix [4]arene adopts a more symmetrical pinched cone conformation in this complex, which is normally observed in methylene-bridged calix [4]arenes.…”

Section: Solid-state Structures Of Ag + and Hg 2+ Complexessupporting

confidence: 75%

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Muravev

Yakupov

Gerasimova

et al. 2022

IJMS

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Sulfur-containing groups preorganized on macrocyclic scaffolds are well suited for liquid-phase complexation of soft metal ions; however, their binding potential was not extensively studied at the air–water interface, and the effect of thioether topology on metal ion binding mechanisms under various conditions was not considered. Herein, we report the interface receptor characteristics of topologically varied thiacalixarene thioethers (linear bis-(methylthio)ethoxy derivative L2, O2S2-thiacrown-ether L3, and O2S2-bridged thiacalixtube L4). The study was conducted in bulk liquid phase and Langmuir monolayers. For all compounds, the highest liquid-phase extraction selectivity was revealed for Ag+ and Hg2+ ions vs. other soft metal ions. In thioether L2 and thiacalixtube L4, metal ion binding was evidenced by a blue shift of the band at 303 nm (for Ag+ species) and the appearance of ligand-to-metal charge transfer bands at 330–340 nm (for Hg2+ species). Theoretical calculations for thioether L2 and its Ag and Hg complexes are consistent with experimental data of UV/Vis, nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffractometry of Ag–thioether L2 complexes and Hg–thiacalixtube L4 complex for the case of coordination around the metal center involving two alkyl sulfide groups (Hg2+) or sulfur atoms on the lower rim and bridging unit (Ag+). In thiacrown L3, Ag and Hg binding by alkyl sulfide groups was suggested from changes in NMR spectra upon the addition of corresponding salts. In spite of the low ability of the thioethers to form stable Langmuir monolayers on deionized water, one might argue that the monolayers significantly expand in the presence of Hg salts in the water subphase. Hg2+ ion uptake by the Langmuir–Blodgett (LB) films of ligand L3 was proved by X-ray photoelectron spectroscopy (XPS). Together, these results demonstrate the potential of sulfide groups on the calixarene platform as receptor unit towards Hg2+ ions, which could be useful in the development of Hg2+-selective water purification systems or thin-film sensor devices.

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Section: Solid-state Structures Of Ag + and Hg 2+ Complexessupporting

confidence: 75%

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Muravev

Yakupov

Gerasimova

et al. 2022

IJMS

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“…A few polyoxo, polyoxometalate, and tetranuclear Cu 4 S 4 based clusters derived (4,4)-connected 2D nets are observed in complexes such as [Th 6 (μ 3 -O) 4 (μ 3 -OH) 4 (HCOO) 12 (DMF) 2 ]·10H 2 O, [Cu 2 (4-Hdpyp) 2 (TeMo 6 O 24 )(H 2 O) 6 ]·4H 2 O (4-dpyp = N , N ′-bis(4-pyridinecarboxamide)-1,3-propane), and [Cu(pzt)] (Hpzt = pyrazine-2-thiol), respectively. − Some other similar nets based on macrocyclic and thiacalix[4]arene units are provided in the literature. ,,− …”

Section: Design Strategiesmentioning

confidence: 99%

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications

et al. 2021

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Among the recent developments in metal-organic frameworks (MOFs), porous layered coordination polymers (CPs) have garnered attention due to their modular nature and tunable structures. These factors enable a number of properties and applications, including gas and guest sorption, storage and separation of gases and small molecules, catalysis, luminescence, sensing, magnetism, and energy storage and conversion. Among MOFs, two-dimensional (2D) compounds are also known as 2D CPs or 2D MOFs. Since the discovery of graphene in 2004, 2D materials have also been widely studied. Several 2D MOFs are suitable for exfoliation as ultrathin nanosheets similar to graphene and other 2D materials, making these layered structures useful and unique for various technological applications. Furthermore, these layered structures have fascinating topological networks and entanglements. This review provides an overview of different aspects of 2D MOF layered architectures such as topology, interpenetration, structural transformations, properties, and applications.

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“…The compounds possess specific internal cavities formed by polygonal frameworks, depending on the number of building blocks, and demonstrate unusual inclusiveness. Based on their structural features, thiacalixarenes have been extensively studied as a platform of host–guest chemistry, such as the extraction of metal ions [ 3 , 4 , 5 , 6 , 7 , 8 , 9 , 10 ], transport materials [ 11 ], catalysts [ 12 ], crystal engineering/supramolecular architectures [ 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ], guest adsorption materials [ 31 , 32 , 33 ], and chemosensors [ 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 ]. Hence, thiacalixarenes show potential as highly useful molecular skeletons for porous molecular recognition materials [ 48 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Characterization of Thiacalix[4]-2,8-thianthrene

2023

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Sulfur-containing macrocycles have attracted substantial interest because they exhibit unique characteristics due to their polygonal ring-shaped skeleton. In this study, a thianthrene-based cyclic tetramer with the sulfur linker, thiacalix[4]-2,8-thianthrene (TC[4]TT), was successfully prepared from a cyclo-p-phenylenesulfide derivative using acid-induced intramolecular condensation. Single crystal X-ray diffraction revealed that TC[4]TT adopts an alternative octagonal form recessed to the inner side. Its internal cavity included small solvents, such as chloroform and carbon disulfide. Due to its polygonal geometry, TC[4]TT laminated in a honeycomb-like pattern with a porous channel. Furthermore, TC[4]TT showed fluorescence and phosphorescence emission in a CH2Cl2 solution at ambient and liquid nitrogen temperatures. Both emission bands were slightly redshifted compared with those of the reference compounds (di(thanthren-2-yl)sulfane (TT2S) and thianthrene (TT)). This work describes a sulfur-containing thiacalixheterocycle-based macrocyclic system with intriguing supramolecular chemistry based on molecular tiling and photophysical properties in solution.

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A Thiacalix Basket and Its Anion‐Dependent 2‐D and 3‐D Silver(I) Coordination Polymers via Exo‐Coordination

Cited by 6 publications

References 50 publications

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications

Synthesis, Structure, and Characterization of Thiacalix[4]-2,8-thianthrene

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