Multinuclear Er-Containing Polyoxometalate Macrocycle Based on Seleno-Bismutho-Tungstate Fragments

A high-nuclear Er-containing macrocyclic seleno-bismutho-tungstate [H<sub>2</sub>N(CH<sub>3</sub>)<sub>2</sub>]<sub>14</sub>Cs<sub>6</sub>H<sub>28</sub>[Er<sub>4</sub>(H<sub>2</sub>O)<sub>8</sub>{Er<sub>3</sub>(H<sub>2</sub>O)<sub>9</sub> (SeBiW<sub>12</sub>O<sub>45</sub>)<sub>2</sub>}<sub>4</sub>]·127H<sub>2</sub>O (<b>1</b>) has been made by the one-pot assembly reaction of Na<sub>2</sub>WO<sub>4</sub>·2H<sub>2</sub>O, Er(NO<sub>3</sub>)<sub>3</sub>·6H<sub>2</sub>O, Bi(NO<sub>3</sub>)<sub>3</sub>·5H<sub>2</sub>O, Na<sub>2</sub>SeO<sub>3</sub>, and dimethylamine hydrochloride in the HOAc-NaOAc buffer solution and structurally characterized. The polyoxoanion of <b>1</b> features an octameric assembly [Er<sub>4</sub>(H<sub>2</sub>O)<sub>8</sub>{Er<sub>3</sub>(H<sub>2</sub>O)<sub>9</sub>(SeBiW<sub>12</sub>O<sub>45</sub>)<sub>2</sub>}<sub>4</sub>]<sup>48-</sup> composed of four dimeric Er<sub>3</sub>(H<sub>2</sub>O)<sub>9</sub>(SeBiW<sub>12</sub>O<sub>45</sub>)<sub>2</sub> subunits alternately connected with four ErO<sub>6</sub>(H<sub>2</sub>O)<sub>2</sub> groups. Notably, the SeBiW<sub>12</sub>O<sub>45</sub> is a brand-new POM fragment formed by two different triangular pyramid heteroatoms, Se and Bi, simultaneously templating tungsten-oxygen groups clustered around them. <b>1</b> represents the first example of lanthanide-containing macrocyclic seleno-bismutho-tungstates and the largest bismutho-seleno-tungstate so far. Further, investigations on the catalytic performance show that compound <b>1</b> is highly efficient for the selective oxidation of various sulfides.

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Journal
Inorganic Chemistry
Published
2025-10-17
DOI
https://doi.org/10.1021/acs.inorgchem.5c03500
Primary Topic
Polyoxometalates: Synthesis and Applications
Type
article
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article

Multinuclear Er-Containing Polyoxometalate Macrocycle Based on Seleno-Bismutho-Tungstate Fragments

Hai‐Lou Li, Nuo Wang, Xinhua Cao, Ruiyu Wang et al.
Inorganic Chemistry
Polyoxometalates: Synthesis and Applications
article

Multinuclear Er-Containing Polyoxometalate Macrocycle Based on Seleno-Bismutho-Tungstate Fragments

Hai‐Lou Li, Nuo Wang, Xinhua Cao, Ruiyu Wang, Lian Chen, Yan Zhang
article en

Abstract

A high-nuclear Er-containing macrocyclic seleno-bismutho-tungstate [H<sub>2</sub>N(CH<sub>3</sub>)<sub>2</sub>]<sub>14</sub>Cs<sub>6</sub>H<sub>28</sub>[Er<sub>4</sub>(H<sub>2</sub>O)<sub>8</sub>{Er<sub>3</sub>(H<sub>2</sub>O)<sub>9</sub> (SeBiW<sub>12</sub>O<sub>45</sub>)<sub>2</sub>}<sub>4</sub>]·127H<sub>2</sub>O (<b>1</b>) has been made by the one-pot assembly reaction of Na<sub>2</sub>WO<sub>4</sub>·2H<sub>2</sub>O, Er(NO<sub>3</sub>)<sub>3</sub>·6H<sub>2</sub>O, Bi(NO<sub>3</sub>)<sub>3</sub>·5H<sub>2</sub>O, Na<sub>2</sub>SeO<sub>3</sub>, and dimethylamine hydrochloride in the HOAc-NaOAc buffer solution and structurally characterized. The polyoxoanion of <b>1</b> features an octameric assembly [Er<sub>4</sub>(H<sub>2</sub>O)<sub>8</sub>{Er<sub>3</sub>(H<sub>2</sub>O)<sub>9</sub>(SeBiW<sub>12</sub>O<sub>45</sub>)<sub>2</sub>}<sub>4</sub>]<sup>48-</sup> composed of four dimeric Er<sub>3</sub>(H<sub>2</sub>O)<sub>9</sub>(SeBiW<sub>12</sub>O<sub>45</sub>)<sub>2</sub> subunits alternately connected with four ErO<sub>6</sub>(H<sub>2</sub>O)<sub>2</sub> groups. Notably, the SeBiW<sub>12</sub>O<sub>45</sub> is a brand-new POM fragment formed by two different triangular pyramid heteroatoms, Se and Bi, simultaneously templating tungsten-oxygen groups clustered around them. <b>1</b> represents the first example of lanthanide-containing macrocyclic seleno-bismutho-tungstates and the largest bismutho-seleno-tungstate so far. Further, investigations on the catalytic performance show that compound <b>1</b> is highly efficient for the selective oxidation of various sulfides.

Inorganic ChemistryVol. 64(42)
Xinyang Normal University (CN)
Openalex Percentile: Top 77%
Polyoxometalates: Synthesis and Applications
DOISourceOpenAlex
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