Multiscale Assembly of [AgS4] Tetrahedrons into Hierarchical Ag–S Networks for Robust Photonic Water

Abstract There is an urgent need to assemble ultrasmall metal chalcogenides (with atomic precision) into functional materials with the required anisotropy and uniformity, on a micro‐ or even macroscale. Here, a delicate yet simple chemistry is developed to produce a silver–sulfur network microplate with a high monodispersity in size and morphology. Spanning from the atomic, molecular, to nanometer, to micrometer scale, the key structural evolution of the obtained microplates includes 2D confinement growth, edge‐sharing growth mode, and thermodynamically driven layer‐by‐layer stacking, all of which are derived from the [AgS 4 ] tetrahedron unit. The key to such a high hierarchical, complex, and accurate assembly is the dense deprotonated ligand layer on the surface of the microplates, forming an infinite surface with high negative charge density. This feature operates at an orderly distance to allow further hierarchical self‐assembly on the microscale to generate columnar assemblies composed of microplate components, thereby endowing the feature of the 1D photonic reflector to water (i.e., photonic water). The reflective color of the resulting photonic water is highly dependent on the thickness of the building blocks (i.e., silver–sulfur microplates), and the coexistent order and fluidity help to form robust photonic water.