DNA has long been used as a template for the construction of helical assemblies of inorganic nanoparticles^1,2,3,4,5. For example, gold nanoparticles decorated with DNA (or with peptides) can create helical assemblies^6,7,8,9. But without such biological ligands, helices are difficult to achieve and their mechanism of formation is challenging to understand^10,11. Atomically precise nanoclusters that are protected by ligands such as thiolate^12,13 have demonstrated hierarchical structural complexity in their assembly at the interparticle and intraparticle levels, similar to biomolecules and their assemblies¹⁴. Furthermore, carrier dynamics can be controlled by engineering the structure of the nanoclusters¹⁵. But these nanoclusters usually have isotropic structures^16,17 and often assemble into commonly found supercrystals¹⁸. Here we report the synthesis of homodimeric and heterodimeric gold nanoclusters and their self-assembly into superstructures. While the homodimeric nanoclusters form layer-by-layer superstructures, the heterodimeric nanoclusters self-assemble into double- and quadruple-helical superstructures. These complex arrangements are the result of two different motif pairs, one pair per monomer, where each motif bonds with its paired motif on a neighbouring heterodimer. This motif pairing is reminiscent of the paired interactions of nucleobases in DNA helices. Meanwhile, the surrounding ligands on the clusters show doubly or triply paired steric interactions. The helical assembly is driven by van der Waals interactions through particle rotation and conformational matching. Furthermore, the heterodimeric clusters have a carrier lifetime that is roughly 65 times longer than that of the homodimeric clusters. Our findings suggest new approaches for increasing complexity in the structural design and engineering of precision in supercrystals.

DNA 长期以来一直被用作构建无机纳米粒子^1,2,3,4,5的螺旋组件的模板。例如，用 DNA（或肽）装饰的金纳米粒子可以产生螺旋组件^6,7,8,9。但如果没有这样的生物配体，螺旋很难实现，它们的形成机制很难理解^10,11。受配体（如硫醇盐^12,13 ）保护的原子级精确纳米簇在颗粒间和颗粒内水平的组装中表现出层次结构复杂性，类似于生物分子及其组装¹⁴。此外，载体动力学可以通过设计纳米团簇的结构来控制¹⁵ . 但这些纳米团簇通常具有各向同性结构^16,17并且经常组装成常见的超晶体¹⁸. 在这里，我们报告了同二聚体和异二聚体金纳米团簇的合成及其自组装成超结构。虽然同二聚体纳米团簇形成逐层的超结构，但异二聚体纳米团簇自组装成双螺旋和四螺旋超结构。这些复杂的排列是两个不同基序对的结果，每个单体一对，其中每个基序与相邻异二聚体上的成对基序结合。这种基序配对让人想起 DNA 螺旋中核碱基的配对相互作用。同时，簇上的周围配体显示出双对或三对的空间相互作用。螺旋组件由范德华相互作用通过粒子旋转和构象匹配驱动。此外，异二聚体簇的载流子寿命大约是同二聚体簇的 65 倍。我们的研究结果提出了增加超晶体结构设计和精度工程复杂性的新方法。