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
N1 - Publisher Copyright:
© 2025 Wiley-VCH GmbH.
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 - http://www.scopus.com/inward/record.url?scp=105005185847&partnerID=8YFLogxK
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 -