{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T12:16:19Z","timestamp":1788351379352,"version":"build-2803163510"},"reference-count":89,"publisher":"Wiley","issue":"28","license":[{"start":{"date-parts":[[2026,5,17]],"date-time":"2026-05-17T00:00:00Z","timestamp":1778976000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,5,17]],"date-time":"2026-05-17T00:00:00Z","timestamp":1778976000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,7,6]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Encapsulation of metal clusters in porous organic cages (POCs) is a promising strategy for metalloenzyme\u2010mimetic catalysts. However, constructing POCs with endogenous metal clusters and achieving atomic\u2010level control over their formation and structural evolution remains a key challenge. Here, we realize the in situ growth of a cubic tetranuclear Ag\u2010halide cluster in an imine\u2010based [4+6] POC (\n                    <jats:bold>\n                      <jats:italic>\u03b1<\/jats:italic>\n                      \u2010Ag\n                      <jats:sub>4<\/jats:sub>\n                      X\n                      <jats:sub>4<\/jats:sub>\n                      @Cage\u20102\n                    <\/jats:bold>\n                    , X = Cl, Br, I) via coordination\u2010driven tandem assembly, monitored by time\u2010resolved mass spectrometry. Upon heating,\n                    <jats:bold>\n                      <jats:italic>\u03b1<\/jats:italic>\n                      \u2010Ag\n                      <jats:sub>4<\/jats:sub>\n                      X\n                      <jats:sub>4<\/jats:sub>\n                      @Cage\u20102\n                    <\/jats:bold>\n                    (X = Cl, Br) undergoes a single\u2010crystal\u2010to\u2010single\u2010crystal transformation, with symmetry breaking via Ag\u2013X bond cleavage and structural transition from cubane to distorted hexahedron (\n                    <jats:italic>\u03b2<\/jats:italic>\n                    phase). This is a rare atomic\u2010level observation of thermally induced structural change of endogenous metal clusters in molecular cages. For CO\n                    <jats:sub>2<\/jats:sub>\n                    electroreduction,\n                    <jats:bold>\n                      <jats:italic>\u03b2<\/jats:italic>\n                      \u2010Ag\n                      <jats:sub>4<\/jats:sub>\n                      X\n                      <jats:sub>4<\/jats:sub>\n                      @Cage\u20102\n                    <\/jats:bold>\n                    reaches 98.7% FE\n                    <jats:sub>CO<\/jats:sub>\n                    at \u22121.05\u00a0V versus RHE with 100\u00a0h stability (outperforming its\n                    <jats:italic>\u03b1<\/jats:italic>\n                    \u2010phase counterpart), a TOF of 100\u00a0060 h\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 500\u00a0mA cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    , ranking among top molecular materials. Mechanistic studies reveal that the\n                    <jats:italic>\u03b2<\/jats:italic>\n                    \u2010Ag\n                    <jats:sub>4<\/jats:sub>\n                    X\n                    <jats:sub>4<\/jats:sub>\n                    structural distortion disrupts charge symmetry of the four Ag atoms and localizes electrons at the bond\u2010cleaved Ag site, lowering the energy barrier for key *COOH intermediate formation. This work offers insights into the dynamic evolution of confined metal clusters via precise host\u2013guest structural engineering.\n                  <\/jats:p>","DOI":"10.1002\/anie.5948094","type":"journal-article","created":{"date-parts":[[2026,5,18]],"date-time":"2026-05-18T03:17:13Z","timestamp":1779074233000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Cage Catalyst: Tandem Assembly and Temperature\u2010Regulated Symmetry Breaking of Endogenous Metal Cluster for Phase\u2010Controlled CO\n                    <sub>2<\/sub>\n                    Electroreduction"],"prefix":"10.1002","volume":"65","author":[{"given":"Yuxiao","family":"Zhang","sequence":"first","affiliation":[{"name":"Department of Chemistry Northeast Normal University  Changchun Jilin China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dongxu","family":"Cui","sequence":"additional","affiliation":[{"name":"State Key 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