Although the electrochemiluminescence (ECL) of metal nanoclusters has been reported, revealing the correlation between structure and ECL at an atomic level is highly challenging. Here, we reported the impact of the metal core of Au₂₀(SAdm)₁₂(CHT)₄ (Au₂₀-AC for short; SAdm = 1-adamantanethiolate; CHT= cyclohexanethiol) and its isomer Au₂₀(TBBT)₁₆ (TBBT = 4-tert-butylthiophenol) on their solution-state and solid-state electrochemiluminescence. In self-annihilation ECL experiments, Au₂₀-AC showed a strong cathodic ECL but a weak anodic ECL, while the ECL signal of Au₂₀(TBBT)₁₆ was weak and barely detectable. Density functional theory (DFT) calculations showed that the Au₇ kernel of [Au₂₀-AC]^- is metastable, weakening its anodic ECL. Au₂₀-AC in solution-state displayed an intense co-reactant ECL in the near-infrared region, which is 7 times higher than that of standard Ru(bpy)₃²⁺. The strongest solid-state ECL emissions of Au₂₀-AC and Au₂₀(TBBT)₁₆ were at 860 and 770 nm, respectively — 15 nm red-shifted for Au₂₀-AC and 20 nm blue-shifted for Au₂₀(TBBT)₁₆, compared to their corresponding solid-state photoluminescence (PL) emissions. This work shows that ECL is significantly affected by the subtle differences of the metal core, and offers a potential basis for sensing and immunoassay platforms based on atomically precise emissive metal nanoclusters.

尽管已经报道了金属纳米团簇的电化学发光 (ECL)，但在原子水平上揭示结构与 ECL 之间的相关性极具挑战性。_{在这里，我们报道了 Au 20} (SAdm) ₁₂ (CHT) ₄ (Au ₂₀ -AC 简称；SAdm = 1-金刚烷硫醇；CHT= 环己硫醇) 及其异构体 Au ₂₀ (TBBT) ₁₆ (TBBT)的金属核影响= 4-叔丁基苯硫酚）对其溶液状态和固态电化学发光的影响。在自湮灭ECL实验中，Au _{20 -AC表现出较强的阴极ECL和较弱的阳极ECL，而Au 20} (TBBT) ₁₆的ECL信号很弱，几乎检测不到。密度泛函理论 (DFT) 计算表明[Au ₂₀ -AC] ^{-的 Au} ₇内核是亚稳态的，削弱了其阳极 ECL。溶液状态的Au ₂₀ -AC 在近红外区域显示出强烈的共反应物 ECL，比标准 Ru(bpy) ₃ ²⁺高 7 倍。_{Au 20} -AC 和 Au ₂₀ (TBBT) ₁₆最强的固态 ECL 发射分别在 860 和 770 nm——Au ₂₀ -AC红移 15 nm， Au ₂₀ (TBBT)蓝移 20 nm ₁₆，与其相应的固态光致发光（PL）发射相比。这项工作表明，ECL 受金属核细微差异的显着影响，并为基于原子级精确发射金属纳米团簇的传感和免疫分析平台提供了潜在的基础。