Structure of the Thiolated Au₁₃₀ Cluster

Abstract

The structure of the recently discovered Au130-thiolate and -dithiolate clusters is explored in a combined experiment-theory approach. Rapid electron diffraction in scanning/transmission electron microscopy (STEM) enables atomic-resolution imaging of the gold core and the comparison with density functional theory (DFT)-optimized realistic structure models. The results are consistent with a 105-atom truncated-decahedral core protected by 25 short staple motifs, incorporating disulfide bridges linking the dithiolate ligands. The optimized structure also accounts, via time-dependent DFT (TD-DFT) simulation, for the distinctive optical absorption spectrum, and rationalizes the special stability underlying the selective formation of the Au130 cluster in high yield. The structure is distinct from, yet shares some features with, each of the known Au102 and Au144/Au146 systems.

Toward the Creation of Functionalized Metal Nanoclusters and Highly Active Photocatalytic Materials Using Thiolate-Protected Magic Gold Clusters

“…119 This type of structure has been confirmed recently by Whetten et al based on theoretical and experimental results. 124 In contrast, the XRD pattern of Au 187 (SC 12 H 25 ) 68 was different from that of Au 102 (SR) 44 and Au 130 (SR) 50 , 119 which suggests that the framework structure of Au 187 (SC 12 H 25 ) 68 is different from that of Au 102 (SR) 44 and Au 130 (SR) 50 . An accurate structural model for Au 187 (SC 12 H 25 ) 68 has not yet been established; however, based on these experimental results, its geometric structure is expected to be determined accurately in the future.…”

Crystal Structure of Barrel-Shaped Chiral Au130(p-MBT)50 Nanocluster

“…17 The same structure model was also proposed by Tlahuice-Flores et al based on scanning transmission electron microscopy (STEM) imaging and density functional theory (DFT) calculation of Au 130 (SR) 50 . 33 There is actually a close relationship between the Au 130 (SR) 50 and the Au 102 (SR) 44 ( Figure S4); that is, both nanoclusters can be included in the family of decahedra, and the Au 130 (SR) 50 can be viewed as an elongated version of the Au 102 (SR) 44 . It is this elongation that creates an additional layer of "foot-holds" in the third shell ( Figure 1C, blue), which makes it possible to form ordered surface patterns of −S−Au−S− ripple stripes in Au 130 (SR) 50 .…”

Correlating the Structure and Optical Absorption Properties of Au76(SR)44 Cluster

“…Recently, significant experimental advances have been made in the structure determination of several magic-sized Au n (SR) m clusters in the size region of about 0.5−2 nm. The atomic structures of Au 133 (SPh-t-Bu) 52 , 12,13 Au 130 (SC 12 H 25 ) 50 , 14,15 Au 102 (p-MBA) 44 , 16 Au 68 (3-MBA) 31−34 (3-MBA = 3-mercaptobenzoic acid), 17 Au 52 (TBBT) 32 (TBBT = 4-tert-butylbenzenethiol), 10 Au 40 (o-MBT) 24 (o-MBT = mercaptobenzothiazole), 18 Au 38 (SCH 2 CH 2 Ph) 24 , 19 Au 25 (SCH 2 CH 2 Ph) 18 − , 20,21 Au 36 (SPht-Bu) 2 4 , 2 2 Au 3 0 S(S-t-Bu) 1 8 , 2 3 Au 2 8 (SPh-t-Bu) 2 0 , 2 4 Au 24 (SCH 2 Ph-t-Bu) 20 , 25 Au 24 (SAdm) 16 , 26 Au 23 (SPh) 16 − , 27 Au 20 (SPh-t-Bu) 16 , 28 and Au 18 (SC 6 H 11 ) 14 29, 30 were determined by single X-ray crystallography and powerful single-particle transmission electron microscopy (SP-TEM). Based on the resolved cluster structures, a generic structural rule denoted as the "divide-and-protect" concept has been summarized.…”

“…According to this concept, 31,32 any Au n (SR) m nanoclusters can be divided into a symmetric gold core covered by interfacial staple motifs (i.e., −SR[AuSR] x −, x = 1, 2, 3, ...). Over the past few years, the "divide-and-protect" concept combined with density functional theory (DFT) computations has led to predictions of a number of cluster structures, including Au 187 (SR) 68 , 33 Au 144 (SR) 60 , 34 Au 68 (SR) 34 , 35 Au 67 (SR) 35 2− , 36 Au 44 (SR) 28 , 37 Au 40 (SR) 24 , 38 Au 38 (SR) 24 , 39,40 Au 25 (SR) 18 − , 41 Au 24 (SR) 20 , 42 Au 20 (SR) 16 , 43 Au 18 (SR) 14 , 44 Au 15 (SR) 13 , 45,46 and Au 12 (SR) 9 + . 47 Although tremendous research efforts have been made on the characterization of atomic structures, an important issue about the structural evolution of Au n (SR) m clusters in the size range 1−2 nm remained elusive.…”