The non-templated empty cavity and its selective anion binding despite having similar shapes

Kim, Kwan Mook; Kim, Ki‐Hyun; Kang, Tae Yi; Park, Jung Su; Song, Rita; Jun, Mira

doi:10.1039/b302648e

Cited by 4 publications

(3 citation statements)

References 21 publications

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“…From the polyhedral perspective, each outer CuO 5 square-based pyramid joins the central pair of octahedra, again through one triangular face. The adoption of a distorted square pyramidal geometry for Cu 2+ containing weaker axial interactions has been seen previously in a number of other Cu 2+ complexes. , …”

Section: Resultssupporting

confidence: 60%

“…The adoption of a distorted square pyramidal geometry for Cu 2+ containing weaker axial interactions has been seen previously in a number of other Cu 2+ complexes. 35 , 36 …”

Section: Resultsmentioning

confidence: 99%

“…The adoption of a distorted square pyramidal geometry for Cu 2+ containing weaker axial interactions has been seen previously in a number of other Cu 2+ complexes. 35,36 The adoption of two structural types, both composed of similar M 2 Zr 2 O 6 cores but with the coordinated metal ions (M n+ ) in different peripheral (1, 3, 5, and 6) or central (2 and 4) positions (type 1 and type 2, Figure 4), suggests that a combination of factors, such as ionic radii, ionic charge, and crystal field stabilization, influences the observed molecular framework. For example, while there is only a small difference in ionic radii between Li + (in 1) and Mg 2+ (in 2) (both ≈ 90 pm for octahedral coordination), 37 the key difference is the charge and charge density of the ions.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis of Heterometallic Zirconium Alkoxide Single-Source Precursors for Bimetallic Oxide Deposition

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Single-source precursors are ubiquitous in a number of areas of chemistry and material science due to their ease of use and wide range of potential applications. The development of new single-source precursors is essential in providing entries to new areas of chemistry. In this work, we synthesize nine new structurally related bimetallic metal-zirconium alkoxides, which can be used as single-source precursors to zirconia-based materials. Detailed analysis of the structures of these complexes provides important insights into the main factors influencing their aggregation. Investigation of the thermal decomposition of these species by TGA, PXRD, SEM, and EDS reveals that they can be used to produce bimetal oxides, such as Li2ZrO3, or a mixture of metal oxides, such as CuO and ZrO2. Significantly, these studies show that thermodynamically unstable forms of zirconia, such as the tetragonal phase, can be stabilized by metal doping, providing the promise for targeted deposition of zirconia materials for specific applications.

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Section: Resultssupporting

confidence: 60%

“…The adoption of a distorted square pyramidal geometry for Cu 2+ containing weaker axial interactions has been seen previously in a number of other Cu 2+ complexes. 35 , 36 …”

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis of Heterometallic Zirconium Alkoxide Single-Source Precursors for Bimetallic Oxide Deposition

et al. 2022

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Flexibility of Inorganic Tennis Ball Structures Inducing Anion Selectivity

Kim

Park

Kang

et al. 2006

Chemistry A European J

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Inorganic tennis balls (ITBs), [[{Pt(betmp)(dach)}(2)Cu](2)(X)][X](3) (in which X=ClO(4) (-) (3), NO(3) (-) (4), Cl(-) (5) and Br(-) (6); dach=trans-1,2-diaminocyclohexane and betmp=bisethylthiomethylidenepropanedioate) and [[{Pt(dteym)(dach)}(2)Cu](2)(PF(6))][PF(6)](3) (7; dteym=1,3-dithiepane-2-ylidenemalonate), were prepared as crystals. Investigation of their X-ray crystal structures revealed that shapes of the cavities in ITBs show significant distortions that depend on the properties of the encapsulated anions. The CuCu* distance was observed to be longest in 7 and shortest in 5, the difference between them being 2.05 A. The flexibility of cavity structures of ITBs makes it possible to encapsulate various anions inside the cavity, while their distortions may be a reason for the difference in the encapsulating ability for anions, that is, anion selectivity. Especially, the distortions observed in 7 are so severe that the encapsulating ability of the cavity for PF(6) (-) is very low compared to other anions. The shapes of ITBs with ClO(4) (-) and BF(4) (-) ions inside their cavities are very similar; however, ClO(4) (-) is encapsulated by the cavity better than BF(4) (-), which is explicable by the difference of metal-anion interactions. This structural study on ITBs gives a clue to the origin of the anion selectivity of the cavity in ITBs previously investigated by (19)F NMR spectroscopy of the ITBs in methanol.

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Sugars to Control Ligand Shape in Metal Complexes: Conformationally Constrained Glycoligands with a Predetermination of Stereochemistry and a Structural Control

et al. 2010

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In coordination chemistry, ligand shape can be used to tune properties, such as metal selectivity, coordination number, electronic structure, redox potential, and metal center stereochemistry including coordination helicates formation, and also to generate cavities for encapsulation. The results presented in this article indicate that two epimeric glycoligands (3 and 4) based on the conformationally restrained xylo- and ribo-1,2-O-isopropylidenefurano scaffolds are preorganized in water through pi-pi stacking due to hydrophobic interactions, as evidenced from excimer observation. The structure obtained in the solid state for one of the Cu(II) complexes (5) is chiral, with an original helical chirality arising from the coiling of the two ligands around the Cu-Cu axis. It shows an unusual double-deck type structure, with pi-pi interaction between two triazoyl-pyridyl rings and with a small cavity between the two Cu(II) ions able to host a bridging water molecule, as suggested by electron paramagnetic resonance. The Cu(II) complex from the epimeric ligand (6) shows similar properties with a mirror-image CD spectrum in the d-d region of the Cu(II). There is a predetermination of chirality at the metal center by the glycoligand induced by the C3 configuration, 6 and 5 being pseudoenantiomers. Interestingly, the stereochemistry at the metal center is here controlled by the combination of pi-stacking and chiral backbone.

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The non-templated empty cavity and its selective anion binding despite having similar shapes

Abstract: An inorganic tennis ball with an empty cavity was formed without any assistance of guest molecules, and found to bind various anions selectively depending on their size and copper-anion interaction strengths without much change of the shapes.

Cited by 4 publications

References 21 publications

Synthesis of Heterometallic Zirconium Alkoxide Single-Source Precursors for Bimetallic Oxide Deposition

Synthesis of Heterometallic Zirconium Alkoxide Single-Source Precursors for Bimetallic Oxide Deposition

Flexibility of Inorganic Tennis Ball Structures Inducing Anion Selectivity

Sugars to Control Ligand Shape in Metal Complexes: Conformationally Constrained Glycoligands with a Predetermination of Stereochemistry and a Structural Control

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