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However, up to now, the packing model of the core and motif has typically been one-to-one. Herein, we present positional isomeric nanoclusters, Au14Cd2-1 and Au14Cd2-2, which feature an identical Au13 icosahedral kernel but differ exclusively in their surface motif arrangements, leading to distinct electronic distributions. This inherent structural fluxionality enables their reversible interconversion mediated by boranes. Capitalizing on distinct metal charge distributions of the isomers, we employed styrene oxidation (highly sensitive to metal valence states) as a mode to probe their catalytic performance. The results show that the electron-deficient Au14Cd2-1 achieves high conversion (93.1%) with epoxide selectivity (77.3%), whereas the electron-rich Au14Cd2-2 gives lower conversion (36.8%) but high benzaldehyde selectivity (88.9%). Mechanistic interrogation via TEMPO\/TPP trapping of key intermediates revealed pathway bifurcation: Au14Cd2-1 follows heterolytic O\u2013O cleavage (metal-oxo pathway), while Au14Cd2-2 undergoes homolytic cleavage (radical pathway). Furthermore, DFT calculations, together with XPS and NMR experiments, revealed stronger styrene binding affinity of Au14Cd2-1, consistent with its higher conversion. This work establishes positional isomerism as an effective strategy to decouple activity and selectivity through independent modulation of substrate binding and O\u2013O bond activation.<\/jats:p>","DOI":"10.1021\/acsnano.6c13482","type":"journal-article","created":{"date-parts":[[2026,9,15]],"date-time":"2026-09-15T13:02:09Z","timestamp":1789477329000},"page":"26302-26310","source":"Crossref","is-referenced-by-count":0,"title":["Structural\nFluxionality of Surface Motifs in Positional\nIsomeric Au14Cd2 Clusters Enables Switchable\nO\u2013O Bond Activation Pathways"],"prefix":"10.1021","volume":"20","author":[{"given":"Yesen","family":"Tan","sequence":"first","affiliation":[{"name":"Xinjiang University , , ,","place":["Urumqi, China, 830017"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yangping","family":"Wang","sequence":"additional","affiliation":[{"name":"Anhui University , , ,","place":["Hefei, China, 230601"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qinzhen","family":"Li","sequence":"additional","affiliation":[{"name":"Anhui University , , ,","place":["Hefei, China, 230601"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2308-5364","authenticated-orcid":true,"given":"Sha","family":"Yang","sequence":"additional","affiliation":[{"name":"Anhui University , , ,","place":["Hefei, China, 230601"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinsong","family":"Chai","sequence":"additional","affiliation":[{"name":"Anhui University , , ,","place":["Hefei, China, 230601"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0009-0267-1354","authenticated-orcid":true,"given":"Baoyu","family":"Huang","sequence":"additional","affiliation":[{"name":"Hunan Engineering University , , ,","place":["Xiangtan, China, 411104"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ling","family":"Huang","sequence":"additional","affiliation":[{"name":"Xinjiang University , , ,","place":["Urumqi, China, 830017"]},{"name":"Nanjing Tech University , , ,","place":["Nanjing, China, 211816"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3068-7160","authenticated-orcid":true,"given":"Manzhou","family":"Zhu","sequence":"additional","affiliation":[{"name":"Anhui University , , ,","place":["Hefei, China, 230601"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,15]]},"reference":[{"key":"2026092909134998600_cit1","doi-asserted-by":"publisher","first-page":"567","DOI":"10.1021\/acs.chemrev.0c00495","article-title":"Toward Active-Site\nTailoring in Heterogeneous Catalysis by Atomically Precise Metal Nanoclusters\nwith Crystallographic Structures","volume":"121","author":"Jin","year":"2021","journal-title":"Chem. 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