Wearing Gigantic Silver Armor on Transition‐Metal‐Containing Polyoxometalates: Formation of Supertetrahedral Intercluster Compounds

Compared to versatile polyoxometalate (POM)-templated Ag clusters, the construction of closed Ag clusters using transition-metal-containing polyoxometalates (TMCPOMs) as anionic templates has, to our knowledge, never been reported. In this work, we have synthesized three TMCPOM-templated gigantic closed Ag clusters, [{(Co<sub>0.58</sub>W<sub>0.42</sub>)<sub>3</sub>(OH)<sub>3</sub>(Ag<sub>0.5</sub>O<sub>3</sub>)(SiW<sub>9</sub>O<sub>34</sub>)}<sub>4</sub>@Ag<sub>114</sub>Br<sub>4</sub>(<sup>t</sup>BuC≡C)<sub>72</sub>]·[SiW<sub>12</sub>O<sub>40</sub>]<sub>2</sub>·10CH<sub>3</sub>CN (1), [{(Cu<sub>0.58</sub>W<sub>0.42</sub>)<sub>3</sub>(OH)<sub>3</sub>(Ag<sub>0.5</sub>O<sub>3</sub>)(SiW<sub>9</sub>O<sub>34</sub>)}<sub>4</sub>@Ag<sub>114</sub>Br<sub>4</sub>(<sup>t</sup>BuC≡C)<sub>72</sub>]·[SiW<sub>12</sub>O<sub>40</sub>]<sub>2</sub> (2), and [{(Co<sub>0.58</sub>W<sub>0.42</sub>)<sub>3</sub>(OH)<sub>3</sub>(Ag<sub>0.5</sub>O<sub>3</sub>)(GeW<sub>9</sub>O<sub>34</sub>)}<sub>4</sub>@Ag<sub>114</sub>Br<sub>4</sub>(<sup>t</sup>BuC≡C)<sub>72</sub>]·[GeW<sub>12</sub>O<sub>40</sub>]<sub>2</sub> (3), using a universal one-pot solvothermal synthetic approach. Single-crystal X-ray diffraction analyses demonstrate that the high-nuclearity transition metal-containing (M = Co/Cu) POMs with idealized T<sub>d</sub> symmetry are closely covered by gigantic Ag armors, representing the largest TMCPOM-templated closed Ag clusters to date. Moreover, compounds 1-3 can form interesting supertetrahedral intercluster packing structures through Columbic and hydrogen bonding interactions between the cationic TMCPOM-templated gigantic {Ag<sub>114</sub>} clusters and the counter [XW<sub>12</sub>O<sub>40</sub>]<sup>4-</sup> (X = Si/Ge) anions. Upon light irradiation, all three compounds exhibited decent photocatalytic CO<sub>2</sub> reduction activity, which is dependent on their different electronic structures.

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Publication Details

Journal
Angewandte Chemie International Edition
Published
2025-04-12
DOI
https://doi.org/10.1002/anie.202505511
Citations
15
Primary Topic
Pigment Synthesis and Properties
Type
article
Field-Weighted Citation Impact
8.06

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article

Wearing Gigantic Silver Armor on Transition‐Metal‐Containing Polyoxometalates: Formation of Supertetrahedral Intercluster Compounds

Ping Bai, Zhimin Wang, Guo‐Yu Yang, Hongjin Lv et al.
15 citations
Angewandte Chemie International Edition
Pigment Synthesis and Properties
8.06
article

Wearing Gigantic Silver Armor on Transition‐Metal‐Containing Polyoxometalates: Formation of Supertetrahedral Intercluster Compounds

Ping Bai, Zhimin Wang, Guo‐Yu Yang, Hongjin Lv, Jiaxin Yang, Yongkang Liu, Yeqin Feng, Mengyun Zhao
article en
15 citations

Abstract

Compared to versatile polyoxometalate (POM)-templated Ag clusters, the construction of closed Ag clusters using transition-metal-containing polyoxometalates (TMCPOMs) as anionic templates has, to our knowledge, never been reported. In this work, we have synthesized three TMCPOM-templated gigantic closed Ag clusters, [{(Co<sub>0.58</sub>W<sub>0.42</sub>)<sub>3</sub>(OH)<sub>3</sub>(Ag<sub>0.5</sub>O<sub>3</sub>)(SiW<sub>9</sub>O<sub>34</sub>)}<sub>4</sub>@Ag<sub>114</sub>Br<sub>4</sub>(<sup>t</sup>BuC≡C)<sub>72</sub>]·[SiW<sub>12</sub>O<sub>40</sub>]<sub>2</sub>·10CH<sub>3</sub>CN (1), [{(Cu<sub>0.58</sub>W<sub>0.42</sub>)<sub>3</sub>(OH)<sub>3</sub>(Ag<sub>0.5</sub>O<sub>3</sub>)(SiW<sub>9</sub>O<sub>34</sub>)}<sub>4</sub>@Ag<sub>114</sub>Br<sub>4</sub>(<sup>t</sup>BuC≡C)<sub>72</sub>]·[SiW<sub>12</sub>O<sub>40</sub>]<sub>2</sub> (2), and [{(Co<sub>0.58</sub>W<sub>0.42</sub>)<sub>3</sub>(OH)<sub>3</sub>(Ag<sub>0.5</sub>O<sub>3</sub>)(GeW<sub>9</sub>O<sub>34</sub>)}<sub>4</sub>@Ag<sub>114</sub>Br<sub>4</sub>(<sup>t</sup>BuC≡C)<sub>72</sub>]·[GeW<sub>12</sub>O<sub>40</sub>]<sub>2</sub> (3), using a universal one-pot solvothermal synthetic approach. Single-crystal X-ray diffraction analyses demonstrate that the high-nuclearity transition metal-containing (M = Co/Cu) POMs with idealized T<sub>d</sub> symmetry are closely covered by gigantic Ag armors, representing the largest TMCPOM-templated closed Ag clusters to date. Moreover, compounds 1-3 can form interesting supertetrahedral intercluster packing structures through Columbic and hydrogen bonding interactions between the cationic TMCPOM-templated gigantic {Ag<sub>114</sub>} clusters and the counter [XW<sub>12</sub>O<sub>40</sub>]<sup>4-</sup> (X = Si/Ge) anions. Upon light irradiation, all three compounds exhibited decent photocatalytic CO<sub>2</sub> reduction activity, which is dependent on their different electronic structures.

Angewandte Chemie International EditionVol. 64(25)
Beijing Institute of Technology (CN), China Institute of Atomic Energy (CN)
National Natural Science Foundation of China, Beijing Institute of Technology, Recruitment Program of Global Experts
Openalex Percentile: Top 2%
Pigment Synthesis and Properties
8.06
DOIOpen Access PDFOpenAlex
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