The ability to modulate nanoparticle (NP) assemblies with atomic precision is still lacking, which hinders us from creating hierarchical NP organizations with desired properties. In this work, a hierarchical fibrous (1D to 3D) assembly of Au NPs (21-gold atom, Au₂₁) is realized and further modulated with atomic precision via site-specific tailoring of the surface hook (composed of four phenyl-containing ligands with a counteranion). Interestingly, tailoring of the associated counterion significantly changes the electrical transport properties of the NP-assembled solids by two orders of magnitude due to the altered configuration of the interacting π-π pairs of the surface hooks. Overall, our success in atomic-level modulation of the hierarchical NP assembly directly evidences how the NP ligands and associated counterions can function to guide the 1D, 2D, and 3D hierarchical self-assembly of NPs in a delicate manner. This work expands nanochemists' skills in rationally programming the hierarchical NP assemblies with controllable structures and properties.

中文翻译：

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以原子精度调节Au纳米粒子的分层纤维组装。

仍然缺乏以原子精度调节纳米粒子（NP）组件的能力，这阻碍了我们创建具有所需特性的层次化NP组织。在这项工作中，Au NP（21金原子，Au _21的层状纤维（1D到3D）组件））通过表面钩（由四个带有抗衡阴离子的含苯基配体组成）的特定位置剪裁来实现并进一步以原子精度进行调节。有趣的是，由于表面钩的相互作用的π-π对的构型的改变，缔合的抗衡离子的剪裁显着地将NP-组装的固体的电传输性质改变了两个数量级。总体而言，我们在分级NP组件的原子级调制方面的成功直接证明了NP配体和相关的抗衡离子如何以微妙的方式指导NP的1D，2D和3D分级自组装。这项工作扩展了纳米化学家对具有可控结构和特性的分级NP组件进行合理编程的技能。