Despite the recent progress on controllable synthesis of alkynyl-protected Au nanoclusters, the effective synthetic means are very limited and the cluster formation process still remains puzzling. Here, we develop a novel synchronous nucleation and passivation strategy to fabricate Au₃₆(PA)₂₄ (PA=phenylacetylenyl) nanoclusters with high yield. In Au₃₆(PA)₂₄ formation process, Au₂₂(PA)₁₈ as key intermediate was identified. Meanwhile, Au₂₂(PA)₁₈ can be synthesized under a low amount of reductant, and by employing more reductants, Au₂₂(PA)₁₈ can turn into Au₃₆(PA)₂₄ eventually. Moreover, the structure evolution from Au₂₂(PA)₁₈ to Au₃₆(PA)₂₄ is proposed, where four Au₁₃ cuboctahedra can yield one Au₂₈ kernel. Finally, the ratiocination is verified by the good accordance between the predicted intermediate/product ratio and the experimental value. This study not only offers a novel synthetic strategy, but also sheds light on understanding the structural evolution process of alkynyl-protected Au nanoclusters at atomic level.

尽管最近在可控制的炔基保护的金纳米簇的合成方面取得了进展，但是有效的合成手段非常有限，并且团簇形成过程仍然令人费解。在这里，我们开发了一种新颖的同步成核和钝化策略，以高产率制备Au ₃₆（PA）₂₄（PA =苯基乙炔基）纳米团簇。在Au ₃₆（PA）_24的形成过程中，确定了Au ₂₂（PA）₁₈为关键中间体。同时，可以在少量的还原剂下合成Au ₂₂（PA）₁₈，并且通过使用更多的还原剂，Au ₂₂（PA）₁₈可以变成Au ₃₆（PA）最终为₂₄。此外，提出了从Au ₂₂（PA）₁₈到Au ₃₆（PA）₂₄的结构演化，其中四个Au ₁₃八面体可以产生一个Au ₂₈核。最后，通过预测的中间产物/产物比率与实验值之间的良好一致性来验证配比。这项研究不仅提供了一种新颖的合成策略，而且为了解炔基保护的金纳米团簇在原子水平上的结构演化过程提供了启示。