Investigating the structural evolution of thiolate protected gold clusters from first-principles

Yong Pei, Xiao Cheng Zeng

Research output: Contribution to journalReview articlepeer-review

183 Scopus citations

Abstract

Unlike bulk materials, the physicochemical properties of nano-sized metal clusters can be strongly dependent on their atomic structure and size. Over the past two decades, major progress has been made in both the synthesis and characterization of a special class of ligated metal nanoclusters, namely, the thiolate-protected gold clusters with size less than 2 nm. Nevertheless, the determination of the precise atomic structure of thiolate-protected gold clusters is still a grand challenge to both experimentalists and theorists. The lack of atomic structures for many thiolate-protected gold clusters has hampered our in-depth understanding of their physicochemical properties and size-dependent structural evolution. Recent breakthroughs in the determination of the atomic structure of two clusters, [Au25(SCH2CH 2Ph)18]q (q = -1, 0) and Au102(p- MBA)44, from X-ray crystallography have uncovered many new characteristics regarding the gold-sulfur bonding as well as the atomic packing structure in gold thiolate nanoclusters. Knowledge obtained from the atomic structures of both thiolate-protected gold clusters allows researchers to examine a more general "inherent structure rule" underlying this special class of ligated gold nanoclusters. That is, a highly stable thiolate-protected gold cluster can be viewed as a combination of a highly symmetric Au core and several protecting gold-thiolate "staple motifs", as illustrated by a general structural formula [Au] a+a′[Au(SR)2]b[Au2(SR) 3]c[Au3(SR)4]d[Au 4(SR)5]e where a, a′, b, c, d and e are integers that satisfy certain constraints. In this review article, we highlight recent progress in the theoretical exploration and prediction of the atomic structures of various thiolate-protected gold clusters based on the "divide-and-protect" concept in general and the "inherent structure rule" in particular. As two demonstration examples, we show that the theoretically predicted lowest-energy structures of Au25(SR) 8- and Au38(SR)24 (-R is the alkylthiolate group) have been fully confirmed by later experiments, lending credence to the "inherent structure rule".

Original languageEnglish (US)
Pages (from-to)4054-4072
Number of pages19
JournalNanoscale
Volume4
Issue number14
DOIs
StatePublished - Jul 21 2012

ASJC Scopus subject areas

  • Materials Science(all)

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