The unique topology and physics of chiral superlattices make their self-assembly from nanoparticles highly sought after yet challenging in regard to (meta)materials^1,2,3. Here we show that tetrahedral gold nanoparticles can transform from a perovskite-like, low-density phase with corner-to-corner connections into pinwheel assemblies with corner-to-edge connections and denser packing. Whereas corner-sharing assemblies are achiral, pinwheel superlattices become strongly mirror asymmetric on solid substrates as demonstrated by chirality measures. Liquid-phase transmission electron microscopy and computational models show that van der Waals and electrostatic interactions between nanoparticles control thermodynamic equilibrium. Variable corner-to-edge connections among tetrahedra enable fine-tuning of chirality. The domains of the bilayer superlattices show strong chiroptical activity as identified by photon-induced near-field electron microscopy and finite-difference time-domain simulations. The simplicity and versatility of substrate-supported chiral superlattices facilitate the manufacture of metastructured coatings with unusual optical, mechanical and electronic characteristics.

手性超晶格的独特拓扑结构和物理特性使得它们从纳米粒子中自组装起来备受追捧，但在（超）材料方面具有挑战性^1,2,3. 在这里，我们展示了四面体金纳米粒子可以从具有角对角连接的类钙钛矿低密度相转变为具有角对边连接和更密集堆积的风车组件。角共享组件是非手性的，而风车超晶格在固体基板上变得强烈镜像不对称，如手性测量所证明的那样。液相透射电子显微镜和计算模型表明纳米粒子之间的范德华力和静电相互作用控制着热力学平衡。四面体之间可变的角到边连接可以微调手性。双层超晶格的域显示出强烈的手性光学活动，如光子诱导的近场电子显微镜和有限差分时域模拟所确定的那样。