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

Yeqin Feng; Mengyun Zhao; Jiaxin Yang; Zhimin Wang; Penghao Bai; Yongkang Liu; Hongjin Lv; Guo Yu Yang

doi:10.1002/anie.202505511

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

Yeqin Feng
, Mengyun Zhao
, Jiaxin Yang
, Zhimin Wang
, Penghao Bai
, Yongkang Liu
, Hongjin Lv^*
, Guo Yu Yang

^*Corresponding author for this work

Beijing Institute of Technology
China National Nuclear Corporation

Research output: Contribution to journal › Article › peer-review

27 Citations (Scopus)

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_0.58W_0.42)₃(OH)₃(Ag_0.5O₃)(SiW₉O₃₄)}₄@Ag₁₁₄Br₄(^tBuC≡C)₇₂]·[SiW₁₂O₄₀]₂·10CH₃CN (1), [{(Cu_0.58W_0.42)₃(OH)₃(Ag_0.5O₃)(SiW₉O₃₄)}₄@Ag₁₁₄Br₄(^tBuC≡C)₇₂]·[SiW₁₂O₄₀]₂ (2), and [{(Co_0.58W_0.42)₃(OH)₃(Ag_0.5O₃)(GeW₉O₃₄)}₄@Ag₁₁₄Br₄(^tBuC≡C)₇₂]·[GeW₁₂O₄₀]₂ (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_d 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 {Ag₁₁₄} clusters and the counter [XW₁₂O₄₀]⁴⁻ (X = Si/Ge) anions. Upon light irradiation, all three compounds exhibited decent photocatalytic CO₂ reduction activity, which is dependent on their different electronic structures.

Original language	English
Article number	e202505511
Journal	Angewandte Chemie - International Edition
Volume	64
Issue number	25
DOIs	https://doi.org/10.1002/anie.202505511
Publication status	Published - 17 Jun 2025
Externally published	Yes

Keywords

Closed Ag cluster
Optical bandgap engineering
Photocatalytic CO reduction
Supertetrahedral intercluster compound
Transition-metal-containing polyoxometalates

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10.1002/anie.202505511

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@article{bf7232c734a24acea2874bb55d8c2733,

title = "Wearing Gigantic Silver Armor on Transition-Metal-Containing Polyoxometalates: Formation of Supertetrahedral Intercluster Compounds",

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, [\{(Co0.58W0.42)3(OH)3(Ag0.5O3)(SiW9O34)\}4@Ag114Br4(tBuC≡C)72]·[SiW12O40]2·10CH3CN (1), [\{(Cu0.58W0.42)3(OH)3(Ag0.5O3)(SiW9O34)\}4@Ag114Br4(tBuC≡C)72]·[SiW12O40]2 (2), and [\{(Co0.58W0.42)3(OH)3(Ag0.5O3)(GeW9O34)\}4@Ag114Br4(tBuC≡C)72]·[GeW12O40]2 (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 Td 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 \{Ag114\} clusters and the counter [XW12O40]4− (X = Si/Ge) anions. Upon light irradiation, all three compounds exhibited decent photocatalytic CO2 reduction activity, which is dependent on their different electronic structures.",

keywords = "Closed Ag cluster, Optical bandgap engineering, Photocatalytic CO reduction, Supertetrahedral intercluster compound, Transition-metal-containing polyoxometalates",

author = "Yeqin Feng and Mengyun Zhao and Jiaxin Yang and Zhimin Wang and Penghao Bai and Yongkang Liu and Hongjin Lv and Yang, \{Guo Yu\}",

note = "Publisher Copyright: {\textcopyright} 2025 Wiley-VCH GmbH.",

year = "2025",

month = jun,

day = "17",

doi = "10.1002/anie.202505511",

language = "English",

volume = "64",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "25",

}

TY - JOUR

T1 - Wearing Gigantic Silver Armor on Transition-Metal-Containing Polyoxometalates

T2 - Formation of Supertetrahedral Intercluster Compounds

AU - Feng, Yeqin

AU - Zhao, Mengyun

AU - Yang, Jiaxin

AU - Wang, Zhimin

AU - Bai, Penghao

AU - Liu, Yongkang

AU - Lv, Hongjin

AU - Yang, Guo Yu

PY - 2025/6/17

Y1 - 2025/6/17

N2 - 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, [{(Co0.58W0.42)3(OH)3(Ag0.5O3)(SiW9O34)}4@Ag114Br4(tBuC≡C)72]·[SiW12O40]2·10CH3CN (1), [{(Cu0.58W0.42)3(OH)3(Ag0.5O3)(SiW9O34)}4@Ag114Br4(tBuC≡C)72]·[SiW12O40]2 (2), and [{(Co0.58W0.42)3(OH)3(Ag0.5O3)(GeW9O34)}4@Ag114Br4(tBuC≡C)72]·[GeW12O40]2 (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 Td 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 {Ag114} clusters and the counter [XW12O40]4− (X = Si/Ge) anions. Upon light irradiation, all three compounds exhibited decent photocatalytic CO2 reduction activity, which is dependent on their different electronic structures.

AB - 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, [{(Co0.58W0.42)3(OH)3(Ag0.5O3)(SiW9O34)}4@Ag114Br4(tBuC≡C)72]·[SiW12O40]2·10CH3CN (1), [{(Cu0.58W0.42)3(OH)3(Ag0.5O3)(SiW9O34)}4@Ag114Br4(tBuC≡C)72]·[SiW12O40]2 (2), and [{(Co0.58W0.42)3(OH)3(Ag0.5O3)(GeW9O34)}4@Ag114Br4(tBuC≡C)72]·[GeW12O40]2 (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 Td 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 {Ag114} clusters and the counter [XW12O40]4− (X = Si/Ge) anions. Upon light irradiation, all three compounds exhibited decent photocatalytic CO2 reduction activity, which is dependent on their different electronic structures.

KW - Closed Ag cluster

KW - Optical bandgap engineering

KW - Photocatalytic CO reduction

KW - Supertetrahedral intercluster compound

KW - Transition-metal-containing polyoxometalates

UR - https://www.scopus.com/pages/publications/105005185847

U2 - 10.1002/anie.202505511

DO - 10.1002/anie.202505511

M3 - Article

AN - SCOPUS:105005185847

SN - 1433-7851

VL - 64

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 25

M1 - e202505511

ER -

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

Abstract

Keywords

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