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

Abstract

One of the latest developments in the field of materials science is the successful synthesis of ultrasmall particles with atomic precision, such as monolayer-protected metal clusters, metal chalcogenides, polyoxometalates, and polynuclear 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.

Layered Organic Metal Chalcogenides (OMCs): From Bulk to Two‐Dimensional Materials

“…Single crystals with thin pellets of Cu(SPhCO 2 Me) can be formed by a redox reaction between Cu(NO 3 ) 2 and p ‐HSPhCO 2 Me under solvothermal conditions [14] . Uniform octagonal plates of NH 4 Ag(SPhCO 2 ) with a lateral dimension of 5.5 μm and a thickness of 150 nm are formed by bottom‐up synthesis [17] …”

“…[22] The structure of Ag(SPh) was first investigated by Mazzoni et al in 2016 using first-principles calculations, [23] and a layered structure was established. The first definite structure of a silver-based OMC is that of NH 4 Ag(SPhCO 2 ) reported by Xu et al [17] Due to the small size of the microplates, this structure could not be resolved by using single-crystal structure analysis. The structure was resolved by 3D ED.…”

Size and Quality Enhancement of 2D Semiconducting Metal–Organic Chalcogenolates by Amine Addition

“…Two-dimensional (2D) hybrid organic–inorganic semiconductors exhibit a unique combination of excitonic behavior, − strong and tunable light–matter interactions, − and potential applications in optoelectronics. , An emerging family within this broader class of materials is 2D metal–organic chalcogenolates (MOCs), − which are synthesized in the form of three-dimensional crystals consisting of 2D layers held together by van der Waals forces. Unlike the more studied ionic 2D lead halide perovskites, − , 2D MOCs are distinguished by the covalent interaction between inorganic and organic components.…”

Multiresponsive Luminescent Behaviors of Assembled Spirocyclic Nonanuclear Silver(I) Clusters

“…[59][60][61][62] Besides, the emission intensity of metal cluster compounds could be enhanced significantly by subtle solvent disturbance to direct the structural ordering of the cluster polydomains. 63 In addition, altering the length of the Au I -SR motifs on the gold nanocluster surface could efficiently adjust the emission wavelength from the visible to the near-infrared II region. 64 Nevertheless, the dominant influential factors for intercluster assemblies and their effects on luminescent properties remain ambiguous.…”