Sulfide Boosting Near-Unity Photoluminescence Quantum Yield of Silver Nanocluster

Silver nanoclusters have emerged as promising candidates for optoelectronic applications, but their room-temperature photoluminescence quantum yield (PLQY) is far from ideal to access cutting-edge device performance. Herein, two supertetrahedral silver nanoclusters with high PLQY in non-degassed solution at room temperature were constructed by interiorly supporting the core with multiple VO₄^3- and E^2- anions as structure-directing agents and exteriorly protecting the core with a rigid ligand shell of PhC≡C^- and Ph₂PE₂^- (E = S, Ag64-S; E = Se, Ag64-Se). Both clusters have similar outer Ag₅₈ tetrahedral cages and [Ag₆E₄@(VO₄)₄] cores, forming a pair of comparable clusters to decrypt the origin of such a high PLQY, particularly in Ag64-S, where the PLQY reached up to 97%. The stronger suppression effect of inner sulfides for nonradiative decay is critical to boost the PLQY to near unity. Transient absorption spectroscopy is employed to confirm the phosphorescence nature. The quadruple-capping assembly mechanism involving Ag₇ secondary building units on a Ag₃₆ truncated tetrahedron was also established by collision-induced dissociation studies. This work not only provides a strategy of core engineering for the controlled syntheses of silver nanoclusters with high PLQY but also deciphers the origin of a near-unity PLQY, which lays a foundation for fabricating highly phosphorescent silver nanoclusters in the future.