Thiolate‐protected gold nanoclusters: structural prediction and the understandings of electronic stability from first principles simulations

Abstract

Thiolate-protected gold nanoclusters (RS-AuNCs) have aroused intensive research interests in field of nanoscience since the breakthroughs in structural determination of Au 102 (SR) 44 , Au 25 (SR) 18 − , and Au 38 (SR) 24 achieved by both theory and experiment. To date, single crystal structures of about 20 thiolateprotected gold nanoclusters had been successfully resolved. The analysis on the structural patterns of the high symmetric cores and the types and numbers of the protecting ligand motifs in these nanoclusters provides deep insight into the inherent structural rule. On this basis, the developed conceptual models not only rationalize the known structures, but also help to predict new ones. Given that the synthesis and crystallization of RS-AuNCs in experiment still remain challenging, theoretical calculations based on density functional theory play a crucial role in structural prediction. Herein, three developed conceptual models for explaining electronic stability and the recent progress of structural prediction through first principles simulations are highlighted. As more atomically precise structures of RS-AuNCs being determined, further understanding of the structure-property relationships is expected to achieve and boost practical applications of metal nanoclusters.

Structure–property relationships on thiolate-protected gold nanoclusters

“…the "R" group in Au n (SR) m ) plays a central role in the stoichiometry of the stable nanocluster synthesized. 13,43,44 Therefore, an experimentalist could utilize these ligand effects to control the number of gold atoms desired within the NC and thus, the resulting electronic where n is the number of Au atoms on the NC. Solid black lines indicate linear fits, whereas shaded regions show 95% confidence intervals.…”

Atomically Precise Gold Nanoclusters: Towards an Optimal Biocompatible System from a Theoretical–Experimental Strategy

“…[ 52 ] By this method, some aspects like general structures, core–shell geometries, and isomerization mechanisms of diverse atomically precise AuNCs have been predicted with high accuracy. [ 17,53,54 ] Furthermore, DFT has supported the development of a molecular mechanics force field for thiolate‐protected AuNCs compatible with the well‐known biomolecular force field AMBER. [ 55 ] This allows investigating the dynamics of the AuNCs in a more realistic biological environment (i.e., including solvent, counterions) by employing classical molecular dynamics (MD) simulations.…”

“…To date, several precise structures have been revealed either by X‐ray diffraction or theoretically predicted by employing density functional theory (DFT) computation. [ 17 ] Combination of theory and experiment has permitted the elucidation of several properties, including electronic structures, luminescence, optical absorption, as well as the structural patterns of their high symmetric cores and their protecting ligand motifs. [ 17,18 ] This well‐defined structural information offers a particularly attractive chance for a better understanding of the structure–property relationships of these intriguing systems and the unique opportunity for highly‐controlled adjustments of specific features in order to increase the desired properties in different applications.…”

New Perspectives on the Electronic and Geometric Structure of Au70S20(PPh3)12 Cluster: Superatomic-Network Core Protected by Novel Au12(µ3-S)10 Staple Motifs

“…Häkkinen et al proposed the divide-and-protect concept [22], and Au-L clusters are composed of Au-core and staple motifs; Au-core is protected by staple motifs. The concept has been widely used to predict and analyze the structures of Au-L clusters [23,24,25,26,27,28,29,30,31,32]. The idea of staple motif has been introduced since the synthesis of Au 102 (SR) 44 cluster, and Jadzinsky et al termed it [1].…”