Structural Characterization of Cerium‐encapsulated Preyssler‐type Phosphotungstate: Additional Evidence of Ce(III) in the Cavity

Shitamatsu, Kota; Kojima, Tatsuhiro; Waddell, Paul G.; Sugiarto, _; Ooyama, Haruka Egawa; Errington, R. John; Sadakane, Masahiro

doi:10.1002/zaac.202100075

Cited by 3 publications

(2 citation statements)

References 53 publications

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“…As for the lanthanide source, lanthanide-containing polyoxometalate (Ln-POM) anions are promising inorganic components [10][11][12][13]. Various types of Ln-POM anions have been synthesized as single crystals under ambient and/or hydrothermal conditions [14][15][16][17]. Hybridizing Ln-POM with organic moieties achieves controllable inorganic-organic hybrid materials in their luminescent properties and material shapes [18][19][20][21].…”

Section: Introductionmentioning

confidence: 99%

Lanthanide-Containing Polyoxometalate Crystallized with Bolaamphiphile Surfactants as Inorganic–Organic Hybrid Phosphors

Ishibashi,

Koike,

Suda

et al. 2024

Inorganics

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Lanthanide elements such as europium exhibit distinctive emissions due to the transitions of inner-shell 4f electrons. Inorganic materials containing lanthanide elements have been widely used as phosphors in conventional displays. The hybridization of lanthanide ions with organic components enables to control of the material’s shapes and properties and broadens the possibility of lanthanide compounds as inorganic–organic materials. Lanthanide ion-containing polyoxometalate anions (Ln-POM) are a promising category as an inorganic component to design and synthesize inorganic–organic hybrids. Several inorganic–organic Ln-POM systems have been reported by hybridizing with cationic surfactants as luminescent materials. However, single-crystalline ordering has not been achieved in most cases. Here, we report syntheses and structures of inorganic–organic hybrid crystals of lanthanide-based POM and bolaamphiphile surfactants with two hydrophilic heads in one molecule. An emissive decatungstoeuropate ([EuW10O36]9−, EuW10) anion was employed as a lanthanide source. The bolaamphiphile counterparts are 1,8-octamethylenediammonium ([H3N(CH2)8NH3]2+, C8N2) and 1,10-decamethylenediammonium ([H3N(CH2)10NH3]2+, C10N2). Both hybrid crystals of C8N2-EuW10 and C10N2-EuW10 were successfully obtained as single crystals, and their crystal structures were unambiguously determined using X-ray diffraction measurements. The photoluminescence properties of C8N2-EuW10 and C10N2-EuW10 were investigated by means of steady-state and time-resolved spectroscopy. The characteristic emission derived from the EuW10 anion was retained after the hybridization process.

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Section: Introductionmentioning

confidence: 99%

Lanthanide-Containing Polyoxometalate Crystallized with Bolaamphiphile Surfactants as Inorganic–Organic Hybrid Phosphors

Ishibashi,

Koike,

Suda

et al. 2024

Inorganics

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“…[27][28][29][30] The Preyssler-type phosphotungstates, [P 5 W 30 O 110 Z n + (H 2 O)] (15À n)À , are constructed using five PO 4 tetrahedra surrounded by thirty WO 6 octahedra, which create a doughnut-shaped structure with an internal cavity space that can encapsulate a cation (Z n + ) in the molecule (Figure 1). Cations such as Na + , [31,32] lanthanide, [4,13,[33][34][35][36] actinide cations, [33][34][35][37][38] Ca 2 + , [4,33,37,39] Y 3 + , [4,33,37] Bi 3 + , [4,19,21,33,39] Ag + , [28][29][30][40][41][42] or K + , [5,6,[43][44][45] can be encapsulated, and the replacement of the encapsulated cation is widely used to tune the properties of the Preyssler compound. An alternative method to tune the properties is the substitution of framework W atoms.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structural Characterization of Multi‐Molybdenum‐Substituted Preyssler‐type Phosphotungstates

et al. 2022

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We report the synthesis of multi-Mo-substituted Preyssler-type phosphotungstates, [P 5 W 30-x Mo x O 110 Na(H 2 O)] 14À , with different amounts of incorporated Mo via the hydrothermal reactions of H 3 PO 4 , Na 2 WO 4 , and Na 2 MoO 4 ; and characterization by 31 P nuclear magnetic resonance (NMR), Fourier-transform infrared (FT-IR), elemental analysis, electrospray ionization-mass spectrometry (ESI-MS), and cyclic voltammetry. The number of substituted Mo increases by increasing the amount of Na 2 MoO 4 in the reaction mixture, and in the [P 5 W 30-x Mo x O 110 Na(H 2 O)] 14À , up to penta-Mo-substituted species can be produced as mixtures of isomers with different Mo numbers and Mo positions. Single crystal X-ray structure analysis and density functional theory calculation indicate that the most suitable substitution position is the belt position.

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Preyssler-type phosphotungstate is a new family of negative-staining reagents for the TEM observation of viruses

Sahiro

Kawato²,

Koike

et al. 2022

Sci Rep

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Transmission electron microscopy (TEM) is an essential method in virology because it allows for direct visualization of virus morphology at a nanometer scale. Negative staining to coat virions with heavy metal ions must be performed before TEM observations to achieve sufficient contrast. Herein, we report that potassium salts of Preyssler-type phosphotungstates (K(15-n)[P5W30O110Mn+], M = Na+, Ca2+, Ce3+, Eu3+, Bi3+, or Y3+) are high-performance negative staining reagents. Additionally, we compare the staining abilities of these salts to those of uranyl acetate and Keggin-type phosphotungstate. The potassium salt of Preyssler-type phosphotungstates has the advantage of not requiring prior neutralization because it is a neutral compound. Moreover, the potassium counter-cation can be protonated by a reaction with H+-resin, allowing easy exchange of protons with other cations by acid–base reaction. Therefore, the counter-cations can be changed. Encapsulated cations can also be exchanged, and clear TEM images were obtained using Preyssler-type compounds with different encapsulated cations. Preyssler-type phosphotungstates may be superior negative staining reagents for observing virus. Polyoxotungstates (tungsten-oxide molecules with diverse molecular structures and properties) are thus promising tools to develop negative staining reagents for TEM observations.

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Structural Characterization of Cerium‐encapsulated Preyssler‐type Phosphotungstate: Additional Evidence of Ce(III) in the Cavity

Cited by 3 publications

References 53 publications

Lanthanide-Containing Polyoxometalate Crystallized with Bolaamphiphile Surfactants as Inorganic–Organic Hybrid Phosphors

Lanthanide-Containing Polyoxometalate Crystallized with Bolaamphiphile Surfactants as Inorganic–Organic Hybrid Phosphors

Synthesis and Structural Characterization of Multi‐Molybdenum‐Substituted Preyssler‐type Phosphotungstates

Preyssler-type phosphotungstate is a new family of negative-staining reagents for the TEM observation of viruses

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