Luminescence is one of the most important properties for metal nanoclusters; however, clearly revealing its origin remains challenging. The different luminescence properties of the two prototypical 8e nanoclusters Au₁₁ and Au₁₃ remain elusive—Au₁₁ is always nonluminescent, whereas Au₁₃ is luminescent. In this work, by using a designed unique aromatic ligand (quinoline-2-thiol), we obtained new atomically precise phosphine-thiolate-protected neutral Au₁₁-SH and cationic Au₁₃-SH. In comparison with the classic phosphine-halide-protected Au₁₁-Cl and Au₁₃-Cl, the Cl-to-thiol alteration triggered room-temperature luminescence of the Au₁₁ core and dramatically modulated that of the Au₁₃ core. Ultrafast ultraviolet/infrared (UV/IR) spectroscopy, which is sensitive to organic aromatic groups, together with ultrafast transient absorption (TA) spectroscopy unprecedently revealed a relaxation process from the ligand to core state affecting the dynamics in excited states and some critical intermediate states favouring efficient room-temperature emission of these nanoclusters. This work provides some new insights into the origin of photoluminescence of metal nanoclusters and opens an avenue to modulate the dynamics of their excited states using aromatic ligands, which would have direct applications in lighting, light harvesting, and photocatalysis.

发光是金属纳米团簇最重要的特性之一。然而，清楚地揭示其起源仍然具有挑战性。两个原型 8e 纳米团簇 Au ₁₁和 Au ₁₃的不同发光特性仍然难以捉摸——Au ₁₁总是不发光的，而 Au ₁₃是发光的。在这项工作中，通过使用设计的独特芳香配体（喹啉-2-硫醇），我们获得了原子级精确的膦硫醇盐保护的中性Au ₁₁ - SH和阳离子Au ₁₃ - SH。与经典卤化膦保护的Au ₁₁ - Cl相比和Au ₁₃ - Cl，Cl 到硫醇的变化引发了 Au ₁₁核心的室温发光，并显着调节了 Au _{13的室温发光}核。对有机芳香基团敏感的超快紫外/红外（UV/IR）光谱与超快瞬态吸收（TA）光谱前所未有地揭示了从配体到核态的弛豫过程，影响激发态和一些关键中间态的动力学有利于这些纳米团簇的有效室温发射。这项工作为金属纳米团簇光致发光的起源提供了一些新的见解，并为使用芳香配体调节其激发态的动力学开辟了一条途径，这将在照明、光捕获和光催化方面有直接的应用。