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Here, we synthesized and structurally characterized a neutral silver cluster, [Ag14(TRZ)12(TPP)3], where TRZ and TPP refer to 6-(dibutylamino)\u20131,3,5-triazine-2,4-dithiolate and triphenylphosphine, respectively. The cluster was synthesized under ambient conditions using a TPP-assisted, solvent-mediated structural transformation from the [Ag31(TRZ)10]2\u2013 precursor cluster. This non-face-centered cubic (non-fcc) cluster features a central Ag5 trigonal bipyramidal core surrounded by a distinct Ag(6+3) tricapped trigonal prismatic (TTP) shell. This type of unconventional metal skeleton differs significantly from the well-known fcc-type Ag14 cluster, which typically has an octahedral Ag6 core and a cubic Ag8 shell. It is also the first metal cluster to be structurally resolved with TRZ ligands. Quantum chemical calculations indicate that although the non-fcc Ag14 skeleton has a lower cohesive energy than the fcc Ag14 analogues, bulky TRZ ligands featuring multiple sulfide linkages and n-butyl chains stabilize it. The as-synthesized Ag14 cluster is non-emissive, but exposure to oxygen converts it into an orange-emitting species. Density functional theory calculations indicate that the TTP Ag(6+3) shell prefers binding with oxygen. Emissive lifetime and femtosecond transient absorption showed that oxygenation provided greater stabilization of excited states than the parent Ag14 cluster. This study presents a new approach for designing metal clusters with unique structural frameworks with unconventional ligand environments and allows for harvesting surface-sensitive electronic properties.<\/jats:p>","DOI":"10.1021\/acsami.6c11805","type":"journal-article","created":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T19:02:05Z","timestamp":1791399725000},"page":"56426-56438","source":"Crossref","is-referenced-by-count":0,"title":["Ag14 Nanocluster Featuring an Unconventional Non-FCC Metal Skeleton and Its Sensitivity to Oxygen"],"prefix":"10.1021","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-5676-0688","authenticated-orcid":true,"given":"Arijit","family":"Jana","sequence":"first","affiliation":[{"name":"Indian Institute of Technology Madras , , ,","place":["Chennai, India, 600036"]},{"name":"Karlsruhe Institute of Technology , , Kaiserstra\u00dfe 12 , ,","place":["Karlsruhe, Germany, 76131"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5723-3970","authenticated-orcid":true,"given":"Akhil S.","family":"Nair","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Indore , , ,","place":["Indore, India, 453552"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5551-7299","authenticated-orcid":true,"given":"Ajay K.","family":"Poonia","sequence":"additional","affiliation":[{"name":"Indian Institute of Science Education and Research Bhopal , , ,","place":["Bhopal, India, 462066"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0006-6535-0011","authenticated-orcid":true,"given":"Jayoti","family":"Roy","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Madras , , ,","place":["Chennai, India, 600036"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0004-0244-0541","authenticated-orcid":true,"given":"Vivek","family":"Yadav","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Madras , , ,","place":["Chennai, India, 600036"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6804-4128","authenticated-orcid":true,"family":"Nonappa","sequence":"additional","affiliation":[{"name":"Tampere University , , ,","place":["Tampere, Finland, FI 33720"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6337-6545","authenticated-orcid":true,"given":"Kumaran Nair Valsala Devi","family":"Adarsh","sequence":"additional","affiliation":[{"name":"Indian Institute of Science Education and Research Bhopal , , ,","place":["Bhopal, India, 462066"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9972-9947","authenticated-orcid":true,"given":"Biswarup","family":"Pathak","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Indore , , ,","place":["Indore, India, 453552"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1325-9228","authenticated-orcid":true,"given":"Stefanie","family":"Dehnen","sequence":"additional","affiliation":[{"name":"Karlsruhe Institute of Technology , , Kaiserstra\u00dfe 12 , ,","place":["Karlsruhe, Germany, 76131"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3174-534X","authenticated-orcid":true,"given":"Thalappil","family":"Pradeep","sequence":"additional","affiliation":[{"name":"Indian Institute of Technology Madras , , ,","place":["Chennai, India, 600036"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,7]]},"reference":[{"key":"2026102108064830200_cit1","doi-asserted-by":"publisher","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","year":"2016","journal-title":"Chem. 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