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

Abstract

We report the structure determination of a large gold nanocluster formulated as Au130(p-MBT)50, where p-MBT is 4-methylbenzenethiolate. The nanocluster is constructed in a four-shell manner, with 55 gold atoms assembled into a two-shell Ino decahedron. The surface is protected exclusively by -S-Au-S- staple motifs, which self-organize into five ripple-like stripes on the surface of the barrel-shaped Au105 kernel. The Au130(p-MBT)50 can be viewed as an elongated version of the Au102(SR)44. Comparison of the Au130(p-MBT)50 structure with the recently discovered icosahedral Au133(p-TBBT)52 nanocluster (where p-TBBT = 4-tert-butylbenzenethiolate) reveals an interesting phenomenon that a subtle ligand effect in the para-position of benzenethiolate can significantly affect the gold atom packing structure, i.e. from the 5-fold twinned Au55 decahedron to 20-fold twinned Au55 icosahedron.

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.…”

Atomic Structure of Self-Assembled Monolayer of Thiolates on a Tetragonal Au92 Nanocrystal

“…[14][15][16] The staple motifs eventually close up and evolve into an octameric Au 8 (SR) 8 ring motif in the Au 20 (SR) 16 nanocluster. 17 For the larger-sized Au 130 (SR) 50 and Au 133 (SR) 52 nanoclusters, 18,19 their extended, curved surfaces are found to be exclusively protected -S-Au-Sstaple motifs, which are further self-aligned and assembled into ripple or helical-like stripe patterns. Such stripe patterns are reminiscent of the rectangular stripes observed in the Au(111) SAMs.…”

“…18,19 (ii) The edge and corner sites can be viewed as being protected respectively by the monomeric and dimeric staple motifs, and they are the natural extension of the surface bridging thiolates, since the staple motifs can be decomposed into simple bridging units. It implies that the staple motifs are favored on the curved surface and at the edge/corner sites.…”

Au108S24(PPh3)16: A Highly Symmetric Nanoscale Gold Cluster Confirms the General Concept of Metalloid Clusters

“…The most prominent examples (only one for each of the elements mentioned above) are [Al 77 (N(SiMe 3 ) 2 ) 20 ] 2À , [4] [Ga 84 (N(SiMe 3 ) 2 ) 20 ] 4À , [5] Ge 18 [Si-(SiMe 3 ) 3 ] 6 , [6] Sn 15 Ar 6 (Ar = NSiMe 3 Dipp; Dipp = 2,6-iPr 2 -C 6 H 3 ), [7] and Pb 10 [Si(SiMe 3 ) 3 ] 6 . [8] These metalloid clusters are synthesized via different synthetic strategies: [Al 77 6 were obtained via the reduction of a M II precursor.…”