Atomic Structure of Self-Assembled Monolayer of Thiolates on a Tetragonal Au₉₂ Nanocrystal

Abstract

Unveiling the ligand binding mode on the crystalline surfaces is important for deciphering the long-standing structural enigma in self-assembled monolayers (SAMs). Here, the binding and patterning structures of thiolates (SR) on the Au(100) crystalline facet are revealed on the basis of the atomic structure of a highly regular, single crystalline Au92(SR)44 nanocrystal. The six exposed facets of this tetragonal nanocrystal give rise to six pieces of "nanoSAMs". We found that thiolates bind to the planar (100) facets of the nanocrystal via a simple bridge-like mode and are assembled into an overlayer with c(2 × 2) symmetry. The Au-S binding mode and translational symmetry in the kernel and on the surface of the Au92 nanocrystal can be generalized infinitely to construct the bulk two-dimensional SAMs and various tetragonal nanocrystals.

Synthesis and Characterization of Gold Silyl Compounds with Different Phosphine or Phosphite Groups for Reduction Reactions

“…In early times alchemists tried to find the "lapis philosophorum", the philosopher's stone, to transmute common metals into gold and silver. [3][4][5][6][7][8][9] Probably, the most prominent examples for metalloid gold clusters are those stabilized by sulfur ligands. [1] Nowadays, the element gold still fascinates chemists and one area of particular interest is the field of metalloid gold clusters.…”

A grand unified model for liganded gold clusters

“…A grand challenge to scientists in this field, however, is the precise determination of atomic structures of liganded gold clusters. To date, atomic structures of tens of liganded gold clusters have been determined via X-ray crystallography56789101112131415161718192021222324252627282930313233343536373839404142434445464748495051525354555657585960616263. Nevertheless, these revelations appear serendipitous as the structural determination largely hinges on availability of single crystals for the liganded gold clusters.…”

Chiral Gold Nanoclusters: Atomic Level Origins of Chirality

“…[64,99,109] however chiral ligand induction is common. [64,99,109] however chiral ligand induction is common.…”

“…The second method is to directly fabricatec hiral nanostructures by templated deposition or growth, [44,45,53] and the third is to assemble achiral Au nanoparticles into chiral assemblies (e.g.,d iscrete oligomers of nanoparticleso rl arge-scale assemblies) with the aid of chiral templates. [65][66][67][68][69][70][71][72][73][74][75][76][77][78][79] More importantly,t he atomic structures of some nanoclusters have been unambiguously mapped out by using single-crystal X-ray crystallography, [64,65,[80][81][82][83][84][85][86][87][88][89][90] and thust he structures have explicitly revealed the atomic-level origin of chirality in the nanoclusters. [1,2,7] Ar ange of atomically precise sizes of gold nanoclusters have recently become assessable, particularly the thiolate-protected ones (denoted Au n (SR) m ,i nw hich n represents the precise number of gold atoms and m is the precise number of surfacet hiolate ligands).…”