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In this work, we have synthesized three TMCPOM\u2010templated gigantic closed Ag clusters, [{(Co\n 0.58<\/jats:sub>\n W\n 0.42<\/jats:sub>\n )\n 3<\/jats:sub>\n (OH)\n 3<\/jats:sub>\n (Ag\n 0.5<\/jats:sub>\n O\n 3<\/jats:sub>\n )(SiW\n 9<\/jats:sub>\n O\n 34<\/jats:sub>\n )}\n 4<\/jats:sub>\n @Ag\n 114<\/jats:sub>\n Br\n 4<\/jats:sub>\n (\n \n t<\/jats:sup>\n <\/jats:italic>\n BuC\u2261C)\n 72<\/jats:sub>\n ]\u00b7[SiW\n 12<\/jats:sub>\n O\n 40<\/jats:sub>\n ]\n 2<\/jats:sub>\n \u00b710CH\n 3<\/jats:sub>\n CN (\n 1<\/jats:bold>\n ), [{(Cu\n 0.58<\/jats:sub>\n W\n 0.42<\/jats:sub>\n )\n 3<\/jats:sub>\n (OH)\n 3<\/jats:sub>\n (Ag\n 0.5<\/jats:sub>\n O\n 3<\/jats:sub>\n )(SiW\n 9<\/jats:sub>\n O\n 34<\/jats:sub>\n )}\n 4<\/jats:sub>\n @Ag\n 114<\/jats:sub>\n Br\n 4<\/jats:sub>\n (\n \n t<\/jats:sup>\n <\/jats:italic>\n BuC\u2261C)\n 72<\/jats:sub>\n ]\u00b7[SiW\n 12<\/jats:sub>\n O\n 40<\/jats:sub>\n ]\n 2<\/jats:sub>\n (\n 2<\/jats:bold>\n ), and [{(Co\n 0.58<\/jats:sub>\n W\n 0.42<\/jats:sub>\n )\n 3<\/jats:sub>\n (OH)\n 3<\/jats:sub>\n (Ag\n 0.5<\/jats:sub>\n O\n 3<\/jats:sub>\n )(GeW\n 9<\/jats:sub>\n O\n 34<\/jats:sub>\n )}\n 4<\/jats:sub>\n @Ag\n 114<\/jats:sub>\n Br\n 4<\/jats:sub>\n (\n \n t<\/jats:sup>\n <\/jats:italic>\n BuC\u2261C)\n 72<\/jats:sub>\n ]\u00b7[GeW\n 12<\/jats:sub>\n O\n 40<\/jats:sub>\n ]\n 2<\/jats:sub>\n (\n 3<\/jats:bold>\n ), using a universal one\u2010pot solvothermal synthetic approach. Single\u2010crystal X\u2010ray diffraction analyses demonstrate that the high\u2010nuclearity transition metal\u2010containing (M\u00a0=\u00a0Co\/Cu) POMs with idealized\n T<\/jats:italic>\n d<\/jats:sub>\n symmetry are closely covered by gigantic Ag armors, representing the largest TMCPOM\u2010templated closed Ag clusters to date. Moreover, compounds\n 1<\/jats:bold>\n \u2212\n 3<\/jats:bold>\n can form interesting supertetrahedral intercluster packing structures through Columbic and hydrogen bonding interactions between the cationic TMCPOM\u2010templated gigantic {Ag\n 114<\/jats:sub>\n } clusters and the counter [XW\n 12<\/jats:sub>\n O\n 40<\/jats:sub>\n ]\n 4\u2212<\/jats:sup>\n (X\u00a0=\u00a0Si\/Ge) anions. Upon light irradiation, all three compounds exhibited decent photocatalytic CO\n 2<\/jats:sub>\n reduction activity, which is dependent on their different electronic structures.\n <\/jats:p>","DOI":"10.1002\/anie.202505511","type":"journal-article","created":{"date-parts":[[2025,4,12]],"date-time":"2025-04-12T02:49:26Z","timestamp":1744426166000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":31,"title":["Wearing Gigantic Silver Armor on Transition\u2010Metal\u2010Containing Polyoxometalates: Formation of Supertetrahedral Intercluster Compounds"],"prefix":"10.1002","volume":"64","author":[{"given":"Yeqin","family":"Feng","sequence":"first","affiliation":[{"name":"MOE 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"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mengyun","family":"Zhao","sequence":"additional","affiliation":[{"name":"MOE 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"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiaxin","family":"Yang","sequence":"additional","affiliation":[{"name":"MOE 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"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhimin","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Radiochemistry China Institute of Atomic Energy Beijing 102413 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Penghao","family":"Bai","sequence":"additional","affiliation":[{"name":"MOE 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"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yongkang","family":"Liu","sequence":"additional","affiliation":[{"name":"MOE 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"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongjin","family":"Lv","sequence":"additional","affiliation":[{"name":"MOE 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"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guo\u2010Yu","family":"Yang","sequence":"additional","affiliation":[{"name":"MOE 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. 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