Ultrafast Size Expansion and Turn‐On Luminescence of Atomically Precise Silver Clusters by Hydrogen Sulfide

Abstract

Abstract The formation of high‐nuclearity silver(I) clusters remains elusive and their potential applications are still underdeveloped. Herein, we firstly prepared a chain‐like thiolated Ag I complex {[Ag 18 (S t Bu) 10 (NO 3 ) 8 (CH 3 CN) 2 (H 2 O) 2 ] ⋅ [Ag 18 (S t Bu) 10 (NO 3 ) 8 (CH 3 CN) 6 ]} n (abbreviated as Ag 18 ) in which two similar Ag 18 clusters are assembled by NO 3 − anions. The solution containing Ag 18 reacted with hydrogen sulfide with controlled concentration, promptly producing another identifiable and bright red‐emitting high‐nuclearity silver(I) cluster, Ag 62 (S) 13 (S t Bu) 32 (NO 3 ) 4 (abbreviated as Ag 62 ). We tracked the transformation using time‐dependent electrospray ionization mass spectrometry (ESI‐MS), UV/Vis absorption and photoluminescence spectra. Based on this cluster transformation, we further developed an ultra‐sensitive turn‐on sensor detecting H 2 S gas with an ultrafast response time (30 s) at a low detection limit (0.13 ppm). This work opens a new way of understanding the growth of metal clusters and developing their luminescent sensing applications.