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Herein, cascade electrochemiluminescence (ECL) is demonstrated for the silver nanocluster Ag\n                    <jats:sub>6<\/jats:sub>\n                    PL\n                    <jats:sub>6<\/jats:sub>\n                    (PL = 4\u2010phenylthiazolidine\u20102\u2010thione) with benzoyl peroxide (BPO) as a coreactant. Three sequential reductions of Ag\n                    <jats:sub>6<\/jats:sub>\n                    PL\n                    <jats:sub>6<\/jats:sub>\n                    enable multielectron charge storage, while BPO reduction generates the oxidizing benzoate radical, which successively oxidizes the three reduced cluster states, enabling cascade ECL. The cascade ECL regime is 460 times more efficient than the first regime, indicating substantial enhancement through the cascade mechanism. The cascade ECL peak wavelength is red\u2010shifted by 60\u00a0nm relative to the neutral\u2010state photoluminescence (665 versus 605\u00a0nm), and photoluminescence under reducing conditions also exhibited a red\u2010shift, supporting the assignment of cascade ECL to reduced nanocluster states. Finite\u2010element simulations of ECL transients were fitted to experimental transients to deconvolute reaction kinetics from species diffusion, yielding rate constants of (2.5 \u00b1 0.6) \u00d7 10\n                    <jats:sup>3<\/jats:sup>\n                    , (3.0 \u00b1 1.2) \u00d7 10\n                    <jats:sup>4<\/jats:sup>\n                    , and (3.0 \u00b1 1.2) \u00d7 10\n                    <jats:sup>4<\/jats:sup>\n                    M\n                    <jats:sup>\u22121<\/jats:sup>\n                    s\n                    <jats:sup>\u22121<\/jats:sup>\n                    for reactions of Ag\n                    <jats:sub>6<\/jats:sub>\n                    PL\n                    <jats:sub>6<\/jats:sub>\n                    <jats:sup>\u2022\u2212<\/jats:sup>\n                    , Ag\n                    <jats:sub>6<\/jats:sub>\n                    PL\n                    <jats:sub>6<\/jats:sub>\n                    <jats:sup>2\u2212<\/jats:sup>\n                    , and Ag\n                    <jats:sub>6<\/jats:sub>\n                    PL\n                    <jats:sub>6<\/jats:sub>\n                    <jats:sup>\u20223\u2212<\/jats:sup>\n                    with the benzoate radical, respectively. These results quantitatively connect multielectron charge storage, charge\u2010state\u2010dependent emission, and cascade ECL kinetics in an atomically precise nanocluster.\n                  <\/jats:p>","DOI":"10.1002\/smll.76035","type":"journal-article","created":{"date-parts":[[2026,9,27]],"date-time":"2026-09-27T17:05:05Z","timestamp":1790528705000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Multielectron Charge Storage Enables Cascade Electrochemiluminescence in an Atomically Precise Silver Nanocluster"],"prefix":"10.1002","author":[{"given":"Zhenzhong","family":"Cai","sequence":"first","affiliation":[{"name":"Department of Chemistry The University of Western Ontario  London ON Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9458-4796","authenticated-orcid":false,"given":"Kai","family":"Li","sequence":"additional","affiliation":[{"name":"Tianjian Laboratory of Advanced Biomedical Sciences Institute of Advanced Biomedical Sciences Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster Materials Green Catalysis Center and College of Chemistry Zhengzhou University  Zhengzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6728-0559","authenticated-orcid":false,"given":"Shuang\u2010Quan","family":"Zang","sequence":"additional","affiliation":[{"name":"Tianjian Laboratory of Advanced Biomedical Sciences Institute of Advanced Biomedical Sciences Henan Key Laboratory of Crystalline Molecular Functional Materials Henan International Joint Laboratory of Tumor Theranostical Cluster Materials Green Catalysis Center and College of Chemistry Zhengzhou University  Zhengzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9252-9320","authenticated-orcid":false,"given":"Zhifeng","family":"Ding","sequence":"additional","affiliation":[{"name":"Department of Chemistry The University of Western Ontario  London ON Canada"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,27]]},"reference":[{"issue":"18","key":"e_1_2_9_2_1","doi-asserted-by":"crossref","first-page":"10346","DOI":"10.1021\/acs.chemrev.5b00703","article-title":"Atomically Precise Colloidal Metal Nanoclusters and Nanoparticles: Fundamentals and Opportunities","volume":"116","author":"Jin R.","year":"2016","journal-title":"Chemical Reviews"},{"issue":"27","key":"e_1_2_9_3_1","doi-asserted-by":"crossref","first-page":"9157","DOI":"10.1073\/pnas.0801001105","article-title":"A Unified View of Ligand\u2010protected Gold Clusters as Superatom Complexes","volume":"105","author":"Walter M.","year":"2008","journal-title":"Proceedings of the National Academy of Sciences"},{"issue":"12","key":"e_1_2_9_4_1","doi-asserted-by":"crossref","first-page":"8208","DOI":"10.1021\/acs.chemrev.6b00769","article-title":"Atomically Precise Clusters of Noble Metals: Emerging Link Between Atoms and Nanoparticles","volume":"117","author":"Chakraborty I.","year":"2017","journal-title":"Chemical Reviews"},{"issue":"5372","key":"e_1_2_9_5_1","doi-asserted-by":"crossref","first-page":"2098","DOI":"10.1126\/science.280.5372.2098","article-title":"Gold Nanoelectrodes of Varied Size: Transition to Molecule\u2010Like Charging","volume":"280","author":"Chen S.","year":"1998","journal-title":"Science"},{"issue":"9","key":"e_1_2_9_6_1","doi-asserted-by":"crossref","first-page":"5759","DOI":"10.1021\/jacs.3c11031","article-title":"N\u2010Heterocyclic Carbene\u2010Stabilized Atomically Precise Metal Nanoclusters","volume":"146","author":"Albright E. 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