A wheel-shaped Zr-substituted phosphotungstate [{Zr(C₂O₄)₂}₃ (PO₄)(P₆W₃₉O₁₅₀)]³⁹⁻ with tunable proton conduction properties

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(22), P. 3043 - 3046

Published: Jan. 1, 2024

A novel wheel-shaped Zr-substituted phosphotungstate, [N(CH 3 ) 4 ] 2 K 16 Na 10.5 H [{Zr(C O } (PO )(P 6 W 39 150 )]⋅45H was prepared, which exhibited a high proton conductivity of 1.18 × 10 −2 S cm −1 at higher temperature 368 K.

Language: Английский

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Constructing a Polyoxometalate-Based Metal–Organic Framework for Photocatalytic Oxidation of Thioethers to Sulfoxides Utilizing In Situ-Generated Superoxide Radicals

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 15, 2025

Developing new photocatalysts for the selective oxidation of thioethers to high-value-added sulfoxides under low-oxygen mild conditions is a promising but challenging strategy. Here, polyoxometalate-based metal–organic framework (POMOF), CoBW12–TPT, was successfully synthesized, wherein continuous π···π stacking interactions and direct coordination bonds not only strengthen framework's stability also accelerate electron transfer. A series experiments theoretical studies, including control experiments, kinetic electrochemical spectroscopic analyses, paramagnetic resonance, revealed synergistic catalytic effect among Co(II) metal centers, BW12O405–, photosensitizer TPT. CoBW12–TPT applied in photocatalytic sulfoxides. Under irradiation, photoinduced transfer POMOF leads generation superoxide radicals from O2, which controls sulfoxide compounds desulfurization reaction shows good activity. In particular, it can be construction some drug molecules such as Modafinil Albendazole Oxide.

Language: Английский

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Aminobenzoic Acid Covalently Modified Polyoxotungstates Based on {XW₆} Clusters with Proton Conductivity Property

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 14, 2025

Three cases of aminobenzoic acid hybrid polyoxotungstates, Na3(H3O)2[(HPW6O21) (O2CC6H4NH2)3]·7H2O (1), K2(H3O)4[(AsW6O21)(O2CC6H4NH2)3]·4H2O (2), and [(H2N(CH3)2]3Na2(H3O)[(SbW6O21) (3), were successfully synthesized. This is the first report successful assembly hexanuclear {XW6} (X = HPIII, AsIII, or SbIII) clusters organic carboxylic (para acid) ligands. All three hybrids feature a common unit composed six-membered {WO6} octahedral ring capped by one {XO3} trigonal pyramid. Furthermore, these possess an extensive three-dimensional network hydrogen bonds, which not only provide high thermal stability but also contribute to excellent proton conductive performances. Simultaneously, based on Hirshfeld partition analysis, combined with interaction between POMs water molecules, transport mechanisms highlighted.

Language: Английский

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A novel square-shaped Zr-substituted polyoxotungstate for the efficient catalytic oxidation of sulfide to sulfone

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 109717 - 109717

Published: March 1, 2024

Language: Английский

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Tetra-Ln³⁺-Implanted Tellurotungstates Covalently Modified by dl-Malic Acid: Proton Conduction and Photochromic Properties

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(19), P. 8791 - 8798

Published: April 30, 2024

Three unique dl-malic acid covalently modified tetra-Ln3+-implanted tellurotungstates [H2(CH3)2]9NaH9[Ln4(H2O)14W6O13(OH)5(Mal)2(B-α-TeW9O33)4]·48H2O [Ln = La3+ (1), Ce3+ (2), Pr3+ (3); H3Mal acid] were fabricated by reacting Na2TeO3, Na2WO4·2H2O, Mal, and LnCl3·6H2O with dimethylamine hydrochloride in an aqueous solution. The most prominent architectural feature of these compounds is the covalent connection mode organic ligand a polyoxometallate backbone, which relatively rare realm polyoxotungstates. tetrameric polyanion can be deemed as four [TeW9O33]8– fragments fused together via intriguing hexanuclearity [W6O13(OH)5(Mal)2Ln4(H2O)14]13+ cluster. Impedance measurements manifest that all three complexes display splendid proton conduction properties, exceptional conductivity for 2 up to 2.48 × 10–2 S·cm–1 under 85 °C 95% relative humidity. Moreover, 1 3 exhibited fast reversible photochromic properties allochroic half-life periods t1/2 1.046 0.544 min, respectively.

Language: Английский

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Synthesis and Characterization of 6-Ti-Substituted Polyoxomolybdate with High Catalytic Activity for Sulfide Oxidation

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(14), P. 6268 - 6275

Published: March 28, 2024

A 6-Ti-substituted polyoxometalate, (NH4)5Cs7Na3H2[Cs@(Ti2GeMo10O39)3]·34H2O (1), was synthesized by reacting (NH4)6Mo7O24·4H2O, GeO2, and TiOSO4 through the conventional aqueous method. Polyanion 1a is composed of three {Ti2GeMo10} segments linked Ti–O–Ti linkages shows a trefoil-shaped structure. Furthermore, one Cs+ cation encapsulated in cavity 1a. Notably, it possesses highest number Ti centers among reported polyoxomolybdates. In addition, serving as high-efficiency heterogeneous catalyst, 1 enables conversion methyl phenyl sulfide within 20 min, yielding 96.4% corresponding sulfoxide with good recyclability.

Language: Английский

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Intensifying Photocatalytic Baeyer–Villiger Oxidation of Ketones with the Introduction of Ru Metalloligands and Bimetallic Units in POM@MOF

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(16), P. 7325 - 7333

Published: April 11, 2024

The synthesis of visible light-responsive and efficient photocatalysts toward green Baeyer–Villiger oxidation organic is extraordinary significance. In this work, we have synthesized two examples light responsive crystalline polyoxometalate@metal–organic framework materials Ru-NiMo Ru-CoMo by introducing Ru metalloligands {CdM3O12} bimetallic units (M = Ni or Co). This the first report metalloligand-modified with nodes, form a three-dimensional directly through coordination bonds between metalloligands. particular, can achieve photocatalytic conversion cyclohexanone to ε-caprolactone in yields as high 95.5% under excitation range λ > 400 nm, achieving turnover number frequency 955 440 h–1, respectively, which are best known for oxidation, while apparent quantum yield measured at 485 nm 4.4%. Moreover, exhibited excellent structural stability recyclability, producing 90.8% after five cycles recycling.

Language: Английский

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Effect of Ligands on Quantum Tunneling of Magnetization for Dysprosium C_4v Single-Molecule Magnets with Theoretical Insights

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(8), P. 3309 - 3318

Published: April 8, 2024

Two mononuclear DyIII-based compounds formulated as [Dy(L-pyra)2(NO3)(H2O)]2·3H2O (1) and [Dy(L-pyri)2(NO3)(CH3OH)] (2) (HL-pyra = N3-(2-pyrazinyl)-3-pyridinecarboxamidrazone; HL-pyri N3-(2-pyridoyl)-3-pyridinecarboxamidrazone) have been synthesized by modifying the ligands with different functional groups. In two compounds, DyIII centers all feature on N4O5 in a spherical capped square-antiprismatic geometry C4v configuration. The magnetic studies showed that 1 2 display single-molecule magnet (SMM) behavior under zero dc field energy barriers of 175.44 322.96 K, respectively. Such an apparent dereference properties was interpreted via ab initio calculations. Theoretical results support axial coordination to be key factor responsible for difference between 2. This work highlights mode Dy–O bond length important factors constructing high-performance SMM.

Language: Английский

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Characterization of the first Peacock–Weakley polyoxometalate containing a transplutonium element: curium bis-pentatungstate [Cm(W₅O₁₈)₂]⁹⁻

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(47), P. 5999 - 6002

Published: Jan. 1, 2024

Leveraging microgram-level techniques, we here present the first transplutonium bis-pentatungstate complex: NaCs 8 Cm(W 5 O 18 ) 2 ·14H (CmW ).

Language: Английский

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{SeO₂(OH)} Bridging Lanthanide-Containing Antimono-Seleno-Tungstates

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(21), P. 9899 - 9906

Published: May 14, 2024

A series of new trigonal pyramidal {SeO2(OH)} bridging lanthanide-containing antimono-seleno-tungstates [H2N(CH3)2]8Na8Cs4H9[Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]2·32H2O [Ln = Tb (1), Dy (2), Ho (3), Er (4)] have been prepared by the synthetic strategy simultaneously using antimonotungstate precursor and simple material in an acidic aqueous solution structurally characterized single-crystal X-ray diffraction, powder IR spectrometry, thermogravimetric analysis. Their molecular structures contain unprecedented hexameric polyoxoanion [Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]229– constituted two equivalent trimeric subunits Ln2W4O9(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33) bridged via μ2-{SeO2(OH)} linkers. Furthermore, catalytic oxidation various aromatic sulfides sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES) compound 3 as heterogeneous catalyst has investigated, exhibiting high conversion selectivity well good stability recyclability.

Language: Английский

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