The discovery of atomically precise nanoclusters is generally unpredictable, and the rational synthesis of nanoclusters guided by the theoretical design is still in its infancy. Here we present a de novo design of Au₃₆(SR)₂₄ nanoclusters, from theoretical prediction to experimental synthesis and characterization of their physicochemical properties. The crystal structure of an Au₃₆(SR)₂₄ nanocluster perfectly matches the simulated structural pattern with Au₄ tetrahedral units along a two-dimensional growth. The Au₃₆(SR)₂₄ nanocluster indeed differs from its structural isomer whose kernel is dissected in an Au₄ tetrahedral manner along a one-dimensional growth. The structural isomerism in the Au₃₆(SR)₂₄ nanoclusters further induces distinct differences in ultrafast electron dynamics and chirality. This work will not only promote the atomically precise synthesis of nanoclusters enlightened by theoretical science, but also open up exciting opportunities for underpinning the widespread applications of structural isomers with atomic precision.

原子精确的纳米团簇的发现通常是无法预测的，并且在理论设计指导下合理合成纳米团簇仍处于起步阶段。在这里，我们介绍从理论预测到实验合成以及其理化特性表征的Au ₃₆（SR）₂₄纳米团簇的从头设计。Au ₃₆（SR）₂₄纳米团簇的晶体结构与二维结构的Au ₄四面体单元的模拟结构图完全匹配。实际上，Au ₃₆（SR）₂₄纳米簇与其结构异构体的结构不同，后者的核被切成Au ₄一面生长的四面体方式。Au ₃₆（SR）₂₄纳米簇中的结构异构现象进一步引起了超快电子动力学和手性的明显差异。这项工作不仅将促进理论科学启发下的纳米团簇的原子精确合成，而且还将为激发具有原子精确度的结构异构体的广泛应用开辟令人兴奋的机遇。