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Herein, we firstly prepared a chain\u2010like thiolated Ag<jats:sup>I<\/jats:sup> complex {[Ag<jats:sub>18<\/jats:sub>(S<jats:sup><jats:italic>t<\/jats:italic><\/jats:sup>Bu)<jats:sub>10<\/jats:sub>(NO<jats:sub>3<\/jats:sub>)<jats:sub>8<\/jats:sub>(CH<jats:sub>3<\/jats:sub>CN)<jats:sub>2<\/jats:sub>(H<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>] \u22c5 [Ag<jats:sub>18<\/jats:sub>(S<jats:sup><jats:italic>t<\/jats:italic><\/jats:sup>Bu)<jats:sub>10<\/jats:sub>(NO<jats:sub>3<\/jats:sub>)<jats:sub>8<\/jats:sub>(CH<jats:sub>3<\/jats:sub>CN)<jats:sub>6<\/jats:sub>]}<jats:sub><jats:italic>n<\/jats:italic><\/jats:sub> (abbreviated as <jats:bold>Ag<jats:sub>18<\/jats:sub><\/jats:bold>) in which two similar <jats:bold>Ag<jats:sub>18<\/jats:sub><\/jats:bold> clusters are assembled by NO<jats:sub>3<\/jats:sub><jats:sup>\u2212<\/jats:sup> anions. The solution containing <jats:bold>Ag<jats:sub>18<\/jats:sub><\/jats:bold> reacted with hydrogen sulfide with controlled concentration, promptly producing another identifiable and bright red\u2010emitting high\u2010nuclearity silver(I) cluster, Ag<jats:sub>62<\/jats:sub>(S)<jats:sub>13<\/jats:sub>(S<jats:sup><jats:italic>t<\/jats:italic><\/jats:sup>Bu)<jats:sub>32<\/jats:sub>(NO<jats:sub>3<\/jats:sub>)<jats:sub>4<\/jats:sub> (abbreviated as <jats:bold>Ag<jats:sub>62<\/jats:sub><\/jats:bold>). We tracked the transformation using time\u2010dependent electrospray ionization mass spectrometry (ESI\u2010MS), UV\/Vis absorption and photoluminescence spectra. Based on this cluster transformation, we further developed an ultra\u2010sensitive turn\u2010on sensor detecting H<jats:sub>2<\/jats:sub>S gas with an ultrafast response time (30\u2005s) at a low detection limit (0.13\u2005ppm). This work opens a new way of understanding the growth of metal clusters and developing their luminescent sensing applications.<\/jats:p>","DOI":"10.1002\/anie.202100006","type":"journal-article","created":{"date-parts":[[2021,1,23]],"date-time":"2021-01-23T12:16:36Z","timestamp":1611404196000},"page":"8505-8509","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":139,"title":["Ultrafast Size Expansion and Turn\u2010On Luminescence of Atomically Precise Silver Clusters by Hydrogen Sulfide"],"prefix":"10.1002","volume":"60","author":[{"given":"Wei\u2010Miao","family":"He","sequence":"first","affiliation":[{"name":"Green Catalysis Center College of Chemistry Zhengzhou University  Zhengzhou 450001 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhe","family":"Zhou","sequence":"additional","affiliation":[{"name":"Green Catalysis Center College of Chemistry Zhengzhou University  Zhengzhou 450001 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