Emergence of hierarchical structural complexities in nanoparticles and their assembly

Abstract

We demonstrate that nanoparticle self-assembly can reach the same level of hierarchy, complexity, and accuracy as biomolecules. The precise assembly structures of gold nanoparticles (246 gold core atoms with 80 p-methylbenzenethiolate surface ligands) at the atomic, molecular, and nanoscale levels were determined from x-ray diffraction studies. We identified the driving forces and rules that guide the multiscale assembly behavior. The protecting ligands self-organize into rotational and parallel patterns on the nanoparticle surface via C-H⋅⋅⋅π interaction, and the symmetry and density of surface patterns dictate directional packing of nanoparticles into crystals with orientational, rotational, and translational orders. Through hierarchical interactions and symmetry matching, the simple building blocks evolve into complex structures, representing an emergent phenomenon in the nanoparticle system.

The fourth crystallographic closest packing unveiled in the gold nanocluster crystal

“…In particular, the structures of gold nanoclusters are of primary significance and have received the most extensive attention in the research community161718192021. However, structure achievements remain limited due to the difficulty of precise size control and structural resolution, especially for relatively large gold nanoclusters2223242526.…”

Self‐Assembly of Chiral Gold Clusters into Crystalline Nanocubes of Exceptional Optical Activity

“…[2] Such as tringent requirement severely limits application of nanoparticles prepared via self-assembly process,because different from molecular synthesis,t op repare monodisperse nanoparticles needs accurate control over nucleation and growth process that is time-and cost-consuming.A nother great challenge in the field of nanoparticle assembly is that the reported assemblies seldom exhibit properties or functions greatly different from those of the individual nanoparticles, and therefore the potential advantages of the ordered assemblies are not demonstrated, only the problems associated with self-assembly. [5] However,until now there are only rare reports on self-assembly of noble-metal clusters into ordered colloidal structures; [6] and more importantly,no new function has been achieved with the assembled structures compared with individual building blocks,a lthough the clusters themselves possess many intriguing optical, electrical, magnetic, and catalytic properties. [5] However,until now there are only rare reports on self-assembly of noble-metal clusters into ordered colloidal structures; [6] and more importantly,no new function has been achieved with the assembled structures compared with individual building blocks,a lthough the clusters themselves possess many intriguing optical, electrical, magnetic, and catalytic properties.…”

Au13(8e): A secondary block for describing a special group of liganded gold clusters containing icosahedral Au13 motifs

“…[18,19] However, this rule of thumb cannot fully describe ligand-protected Au nanoclusters. [20] In 2008, Walter and Hä kkinen et al proposed the superatom complex (SAC) model to explain high stabilities of some spherical ligand-protected Au nanoclusters with total count of valence electrons of 2,8,18,34,58 (electronic shell closing) on basis of the jellium model. [21] Later, Cheng et al developed a super valence bond (SVB) model [22] and a superatom network (SAN) model [23] to interpret high stabilities of certain nonspherical thiolate-protected Au nanoclusters based on the adaptive natural density partitioning (AdNDP) analysis.…”

“…[1][2][3][4] From 1970s to the present, a large number of liganded gold nanoclusters have been synthesized and their structures have been determined via X-ray crystallography [5][6][7][8][9][10] or predicted by density functional theory (DFT) computation. [11][12][13][14][15][16][17] Although total structural determination and prediction of numerous ligand-protected gold nanoclusters have been accomplished, understanding of structural stabilities and evolution of many seemingly-unrelated structures of the liganded gold nanoclusters remains to be an active area of research.…”