Ligand-induced change of the crystal structure and enhanced stability of the Au₁₁ nanocluster

Abstract

In this paper, we report a highly stable gold nanocluster co-protected by the selenophenol and 1,5bis(diphenylphosphino)pentane (L 5 for short) ligands, formulated as [Au 11 (L 5 ) 4 (SePh) 2 ] + . The structure of this nanocluster is determined by X-ray crystallography. The L 5 -ligands are in the form of "Au-PPh 2 (CH 2 ) 5 Ph 2 P-Au", similar to the "staple motif" in the Au n (SR) m nanoclusters. The purity of this nanocluster is confirmed by electrospray ionization mass spectrometry (ESI-MS) and the thermogravimetric analysis (TGA). Moreover, we have also systematically investigated the stability of the [Au 11 (L 5 ) 4 (SePh) 2 ] + (Au 11 -Se for short). The resultsshow that Au 11 -Se is significantly more stable than both Au 11 (PPh 3 ) 7 Cl 3 (Au 11 -7 for short) and [Au 11 (PPh 3 ) 8 Cl 2 ] Cl (Au 11 -8 for short), even in the presence of excess thiol (RSH). This work will provide a new opportunity for future wide research on gold nanoclusters.

Polymorphism of Phosphine-Protected Gold Nanoclusters: Synthesis and Characterization of a New 22-Gold-Atom Cluster

“…[ 45,63 ] On the other hand, for the same gold core structure, or even different gold cores that share the same gold building units, the UV-Vis spectra always show similar absorption features, regardless of the phosphine ligands. [ 46,64 ] Their UV-Vis-NIR spectra are very similar and show strong absorption peaks at ≈310 and 420 nm, and weak peaks at ≈380 and 515 nm, as documented in [ 50,51 ] which consists of an icosahedral Au 13 building unit with an extra Au 7 clamp as a new layer. It was observed that the [Au 20 (PP 3 ) 4 ]Cl 4 cluster gave similar UV-Vis-NIR spectral features as the previously known icosahedral cluster, [Au 13 (dppe) 5 Cl 2 ]Cl 3 (dppe = 1,2-bis(diphenyl-phosphino)ethane, C 26 H 24 P 2 ) at ≈360 and ≈490 nm.…”

Polymorphism of Au11(PR3)7Cl3 clusters: understanding C–H⋯π interaction and C–H⋯Cl–C van der Waals interaction on cluster assembly by surface modification

“…[11][12][13] Ligands play a crucial role in the stabilization of nanoclusters. [14][15][16][17] The non-covalent interactions between surface ligands not only alter properties of clusters but also have signicant effects on nanocluster assembly and selfassembly. [18][19][20][21][22][23][24][25][26][27][28][29][30] For instance, Wu and co-workers demonstrated that C-H/p interactions facilitated the chiral arrangement of ligands, and the assembled ligands presented rotational and parallel patterns on the surface of the nanoparticles.…”

“…34,35 To date, a series of Au 11 (PR 3 ) Cl 3 nanoclusters with adjustable ligands have been extensively studied comparing with other nanoclusters. 15,[36][37][38][39] Therefore, Au 11 (PR 3 )Cl 3 clusters are chosen as models to investigate noncovalent interactions in the crystallization of nanoclusters by surface modication.…”

Ligand-Protected Gold Clusters

“…For these reasons, SR ligands have become the most common choice for use with gold clusters . Recently, the synthesis of gold clusters protected by other chalcogenates (selenolate (SeR) or tellurolate (TeR); Figure 1(c)) [41][42][43][44][45][46][47][48][49][50][51], by alkynes [52][53][54], or by two kinds of ligand ( Figure 1(d)) [55][56][57][58][59] has also been reported. In this chapter, we focus on gold clusters protected by chalcogenates (Au n (XR) m ; XR = SR, SeR, or TeR) and describe the synthetic procedures, geometric/electronic structures, and physical and chemical properties of these compounds.…”

“…Moreover, the physical and chemical properties of these gold clusters are greatly affected by the type of functional group of the protecting ligand. The ligand exchange [2,10,11,29,30,34,47,48,59]).…”