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Here, we report a thiacalix[4]arene\u2010protected Cu(I)\u2010alkynide cluster, {NaCu\n                    <jats:sub>35<\/jats:sub>\n                    (TC4A)\n                    <jats:sub>4<\/jats:sub>\n                    (Ph\u2010C\u2261C)\n                    <jats:sub>20<\/jats:sub>\n                    } (\n                    <jats:bold>\n                      Cu\n                      <jats:sub>35<\/jats:sub>\n                    <\/jats:bold>\n                    ), which exhibits remarkable structural plasticity. This metastable cluster can grow into a\n                    <jats:bold>\n                      Cu\n                      <jats:sub>36<\/jats:sub>\n                    <\/jats:bold>\n                    species via ion substitution or undergo thermal\u2010induced fragmentation to form a smaller\n                    <jats:bold>\n                      Cu\n                      <jats:sub>14<\/jats:sub>\n                    <\/jats:bold>\n                    cluster. Under thermal etching by Ag\n                    <jats:sup>+<\/jats:sup>\n                    ion, structural reconstruction is triggered, leading to the formation of the bimetallic\n                    <jats:bold>\n                      Cu\n                      <jats:sub>14<\/jats:sub>\n                      Ag\n                      <jats:sub>6<\/jats:sub>\n                    <\/jats:bold>\n                    and\n                    <jats:bold>\n                      Cu\n                      <jats:sub>40<\/jats:sub>\n                      Ag\n                      <jats:sub>16<\/jats:sub>\n                    <\/jats:bold>\n                    clusters. The structural reorganization significantly alters the catalytic outcomes in electrocatalytic CO\n                    <jats:sub>2<\/jats:sub>\n                    reduction. Although the monometallic\n                    <jats:bold>\n                      Cu\n                      <jats:sub>35<\/jats:sub>\n                    <\/jats:bold>\n                    and\n                    <jats:bold>\n                      Cu\n                      <jats:sub>14<\/jats:sub>\n                    <\/jats:bold>\n                    favor gaseous CH\n                    <jats:sub>4<\/jats:sub>\n                    \/C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    production, the bimetallic\n                    <jats:bold>\n                      Cu\n                      <jats:sub>14<\/jats:sub>\n                      Ag\n                      <jats:sub>6<\/jats:sub>\n                    <\/jats:bold>\n                    demonstrates remarkable selectivity for ethanol synthesis. Notably,\n                    <jats:bold>\n                      Cu\n                      <jats:sub>14<\/jats:sub>\n                      Ag\n                      <jats:sub>6<\/jats:sub>\n                    <\/jats:bold>\n                    achieves an impressive Faradaic efficiency (FE) of 49.27% for ethanol production, alongside a high partial current density of \u221267.94\u00a0mA cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    . This marks the highest ethanol selectivity reported to date for atomically precise cluster catalysts. Mechanistic investigations reveal that, compared to homometallic Cu\u22efCu dual sites (which typically favor C\n                    <jats:sub>2<\/jats:sub>\n                    H\n                    <jats:sub>4<\/jats:sub>\n                    ), the unique Ag\u22efCu\u22efCu trimetallic microstructure in\n                    <jats:bold>\n                      Cu\n                      <jats:sub>14<\/jats:sub>\n                      Ag\n                      <jats:sub>6<\/jats:sub>\n                    <\/jats:bold>\n                    is more thermodynamically favorable for asymmetric C\u2500C coupling between *CHO and *OCH\n                    <jats:sub>2<\/jats:sub>\n                    , facilitating the formation of the key *CHO\u2212*OCH\n                    <jats:sub>2<\/jats:sub>\n                    intermediate, which drives the ethanol\u2010selective pathway.\n                  <\/jats:p>","DOI":"10.1002\/anie.202511232","type":"journal-article","created":{"date-parts":[[2025,7,8]],"date-time":"2025-07-08T10:35:17Z","timestamp":1751970917000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":27,"title":["Ag\u207a\u2010Mediated Structural Reconstruction of a Metastable Cu\n                    <sub>35<\/sub>\n                    Cluster Toward Cu\u2013Ag Heterometallic Architectures for Superior Electrocatalytic CO\n                    <sub>2<\/sub>\n                    \u2010to\u2010Ethanol Conversion"],"prefix":"10.1002","volume":"64","author":[{"given":"Xin\u2010Yu","family":"Chen","sequence":"first","affiliation":[{"name":"College of Chemistry and Chemical Engineering Central South University  Changsha Hunan 410083 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lan\u2010Yan","family":"Li","sequence":"additional","affiliation":[{"name":"School of Resources and Environment Hunan University of Technology and Business  Changsha 410205 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Lan\u2010Cheng","family":"Zhao","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Shandong University of Science and Technology  Zibo Shandong 255000 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qing\u2010Yi","family":"Liu","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Central South University  Changsha Hunan 410083 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dang\u2010Dang","family":"Ding","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering Central South University  Changsha Hunan 410083 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Li\u2010Li","family":"Zhang","sequence":"additional","affiliation":[{"name":"Qingdao Institute of BioEnergy and Bioprocess Technology Chinese Academy of Sciences  Qingdao 266000 P.R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiao\u2010Yan","family":"Sun","sequence":"additional","affiliation":[{"name":"Qingdao Institute of BioEnergy and Bioprocess Technology Chinese Academy of Sciences  Qingdao 266000 P.R. 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