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Wearing Gigantic Silver Armor on Transition-Metal-Containing Polyoxometalates: Formation of Supertetrahedral
Yeqin Feng1, Mengyun Zhao1, Jiaxin Yang1
1MOE Key Laboratory of Cluster Science, Beijing Key Laboratory of Photoelectric/Electrophotonic Conversion Materials, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing, 102488, P.R. China.
None:
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.
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