Observation of Body‐Centered Cubic Gold Nanocluster

Abstract

The structure of nanoparticles plays a critical role in dictating their material properties. Gold is well known to adopt face-centered cubic (fcc) structure. Herein we report the first observation of a body-centered cubic (bcc) gold nanocluster composed of 38 gold atoms protected by 20 adamantanethiolate ligands and two sulfido atoms ([Au38S2(SR)20], where R=C10H15) as revealed by single-crystal X-ray crystallography. This bcc structure is in striking contrast with the fcc structure of bulk gold and conventional Au nanoparticles, as well as the bi-icosahedral structure of [Au38(SCH2CH2Ph)24]. The bcc nanocluster has a distinct HOMO-LUMO gap of ca. 1.5 eV, much larger than the gap (0.9 eV) of the bi-icosahedral [Au38(SCH2CH2Ph)24]. The unique structure of the bcc gold nanocluster may be promising in catalytic applications.

The fourth crystallographic closest packing unveiled in the gold nanocluster crystal

“…The large staple motif Au 8 (SR) 8 was reported in Au 20 (SR) 16 nanocluster27, but the question remains whether there is a larger staple motif. Although thiolate or sulfido (-S-) can be found in the surface of gold nanoclusters as protecting ligands, both thiolate sulfur and sulfido (-S-) are always three-coordinate (mainly μ 2 -S and rarely μ 3 -S)2829, naturally raising the question of whether there are sulfurs with any other coordination numbers in gold nanoclusters. Notably, four-coordinate μ 4 -S and five-coordinate μ 4 -S have been reported in Cr(III) and Cu(I) complexes3031, respectively, but such high-coordinate sulfur has not been found in Au–S interfaces (not limited to gold nanoclusters).…”

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.…”

Observation of Non‐FCC Copper in Alkynyl‐Protected Cu53Nanoclusters

“…For example, a thiolate stabilized Au 36 NC exhibits an ABC packing mode (FCC), while a Au 18 kernel was assembled into a ABAB pattern (HCP) in a Au 30 NC . Even body‐centered cubic (BCC) Au 38 NC was observed . The decisive role of ligands on the kernel structure has also been exemplified by various Ag NCs .…”