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

Area of Science:

• Nanomaterials Science
• Computational Chemistry
• Solid-State Chemistry

Background:

• Physicochemical properties of nano-sized metal clusters depend on atomic structure and size.
• Thiolate-protected gold nanoclusters (<2 nm) are a significant research area.
• Determining precise atomic structures of these clusters remains a challenge, hindering property understanding.

Purpose of the Study:

• To review theoretical progress in predicting atomic structures of thiolate-protected gold clusters.
• To highlight the
• divide-and-protect
• concept and the
• inherent structure rule
• for understanding these nanoclusters.
• To demonstrate the validity of theoretical predictions through experimental confirmation.

Main Methods:

• X-ray crystallography for atomic structure determination.
• Theoretical exploration and prediction of nanocluster structures.
• Analysis of gold-sulfur bonding and atomic packing.

Main Results:

• Breakthroughs in determining atomic structures of specific gold clusters ([Au(25)(SCH(2)CH(2)Ph)(18)](q) and Au(102)(p-MBA)(44)).
• Uncovered new characteristics of gold-sulfur bonding and atomic packing.
• Established an "inherent structure rule" viewing clusters as a gold core with staple motifs.

Conclusions:

• The "inherent structure rule" provides a general framework for understanding thiolate-protected gold nanoclusters.
• Theoretical predictions of lowest-energy structures for Au(25)(SR)(8)(-) and Au(38)(SR)(24) were experimentally validated.
• This work advances the understanding of structure-property relationships in gold nanoclusters.