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all-organic ligand\u2013protected metal nanoclusters have recently attracted widespread attention. Platinum (Pt) remains an indispensable metal in various fields, particularly in catalysis and cancer therapeutics. However, all-organic ligand\u2013protected Pt nanoclusters are rarely reported due to substantial synthesis challenges, which have hindered progress in Pt nanocluster research and their practical applications. Herein, we report the successful synthesis of the largest all-organic ligand\u2013protected Pt nanocluster to date, [Pt19(NapNC)27][PF6]2 (abbreviated as Pt19; NapNC: isocyanonaphthalene), achieved through the development of a ligand-exchange method. Single-crystal X-ray diffraction (SC-XRD) revealed a face-centered cubic (FCC), nonequivalent structure that has not been previously documented for all-organic ligand\u2013protected Pt nanoclusters. Compared with its partially organic parent nanoclusters, this novel nanocluster exhibits considerably enhanced stability in both the ground and excited states. Furthermore, the Pt19 nanocluster demonstrates superior activity in the electrocatalytic methanol oxidation reaction (MOR) relative to its parent nanoclusters and commercial Pt\/C. Based on its well-defined structure, we gained deep insights into the exceptional MOR activity of Pt19 and revealed, for the first time, the steric and electronic preferences of the active sites for electrocatalytic MOR.<\/jats:p>","DOI":"10.1021\/jacs.6c13812","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T21:25:21Z","timestamp":1788470721000},"page":"44649-44658","source":"Crossref","is-referenced-by-count":0,"title":["Atomically Precise\nPt19: The Largest All-Organic\nLigand\u2013Protected Platinum Nanocluster with Enhanced Stability\nand Electrocatalytic Activity"],"prefix":"10.1021","volume":"148","author":[{"given":"Zongbing","family":"He","sequence":"first","affiliation":[{"name":"Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences , , , ,","place":["Hefei, Anhui, P. R. China, 230031"]},{"name":"University of Science and Technology of China , , ,","place":["Hefei, P. R. 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China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5430-8949","authenticated-orcid":true,"given":"Chengming","family":"Wang","sequence":"additional","affiliation":[{"name":"University of Science and Technology of China , , , ,","place":["Hefei, Anhui, P. R. China, 230026"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shouguo","family":"Wang","sequence":"additional","affiliation":[{"name":"Anhui University , , ,","place":["Hefei, China, 230601"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shengli","family":"Zhuang","sequence":"additional","affiliation":[{"name":"Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences , , , ,","place":["Hefei, Anhui, P. R. China, 230031"]},{"name":"University of Science and Technology of China , , ,","place":["Hefei, P. R. China, 230026"]},{"name":"Anhui University , , ,","place":["Hefei, P. R. China, 230601"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3036-027X","authenticated-orcid":true,"given":"Qingqing","family":"Yang","sequence":"additional","affiliation":[{"name":"Anhui University , , ,","place":["Hefei, China, 230601"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5472-4846","authenticated-orcid":true,"given":"Lingwen","family":"Liao","sequence":"additional","affiliation":[{"name":"Institute of Solid State Physics, HFIPS, Chinese Academy of Sciences , , , ,","place":["Hefei, Anhui, P. R. China, 230031"]},{"name":"University of Science and Technology of China , , ,","place":["Hefei, P. R. China, 230026"]},{"name":"Anhui University , , ,","place":["Hefei, P. R. 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