Synthesis, single crystal X-ray analysis, and TEM for a single-sized Au11 cluster stabilized by SR ligands: The interface between molecules and particles

Nunokawa, Keiko; Onaka, Satoru; Ito, Mitsuhiro; Horibe, Makoto; Yonezawa, Tetsu; Nishihara, Hiroshi; Ozeki, Tomoji; Chiba, Hirokazu; Watase, Seiji; Nakamoto, Masami

doi:10.1016/j.jorganchem.2005.09.043

Cited by 70 publications

(86 citation statements)

References 29 publications

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“…The undecagold compounds generally have the formula Au 11 (PR 3 ) 7 X 3 , where X ϭ halide or thiolate, and the gold skeleton often has an approximate C 3v symmetry. We have investigated here the electronic structure of clusters Au 11 (PH 3 ) 7 (SMe) 3 and Au 11 (PH 3 ) 7 Cl 3 , which are homologous models for a recently reported thiolate-stabilized cluster Au 11 (S-4-NC 5 H 4 ) 3 (PPh 3 ) 7 (17). The optimized structures of these clusters are shown in Fig.…”

Section: Resultsmentioning

confidence: 96%

A unified view of ligand-protected gold clusters as superatom complexes

Walter¹,

Akola

Lopez-Acevedo³

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

1,564

2,167

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Synthesis, characterization, and functionalization of self-assembled, ligand-stabilized gold nanoparticles are long-standing issues in the chemistry of nanomaterials. Factors driving the thermodynamic stability of well documented discrete sizes are largely unknown. Herein, we provide a unified view of principles that underlie the stability of particles protected by thiolate (SR) or phosphine and halide (PR 3, X) ligands. The picture has emerged from analysis of large-scale density functional theory calculations of structurally characterized compounds, namely Au 102(SR)44, Au39(PR3)14X6 ؊ , Au 11(PR3)7X3, and Au13(PR3)10X2 3؉ , where X is either a halogen or a thiolate. Attributable to a compact, symmetric core and complete steric protection, each compound has a filled spherical electronic shell and a major energy gap to unoccupied states. Consequently, the exceptional stability is best described by a ''noble-gas superatom'' analogy. The explanatory power of this concept is shown by its application to many monomeric and oligomeric compounds of precisely known composition and structure, and its predictive power is indicated through suggestions offered for a series of anomalously stable cluster compositions which are still awaiting a precise structure determination.density functional theory ͉ monolayer-protected cluster

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Section: Resultsmentioning

confidence: 96%

A unified view of ligand-protected gold clusters as superatom complexes

Walter¹,

Akola

Lopez-Acevedo³

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

1,564

2,167

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“…(31) (Fig. 1) [42], which is obviously different from the icosahedron-based structures with approximately C 3v symmetry found in the conventional Au 11 (PAr 3 ) 10 clusters for various combinations of phosphine, sub-ligands, and counter anion [28,29,33,47,65,84,88,99] (Table 1 and 23 and 30 in Fig. 1).…”

Section: N # 13mentioning

confidence: 96%

Phosphine-Coordinated Pure-Gold Clusters: Diverse Geometrical Structures and Unique Optical Properties/Responses

Konishi

2014

Structure and Bonding

115

125

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Synthetic techniques, geometrical structures, and electronic absorption spectra of phosphine-coordinated pure-gold molecular clusters (PGCs) accumulated over 40 years are comprehensively collected especially for those with unambiguous X-ray crystal structures available. Inspection of the electronic absorption spectra from geometrical aspects reveals that their optical properties are highly dependent on the cluster geometries rather than the nuclearity. Recent examples of unusual clusters that show unique color / photoluminescence properties and their utilization for stimuli-responsive modules are also presented.

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“…The charge state of 1 was assigned as neutral based on the fact that the lattice volumes of the crystals prepared in the presence and absence of PF 6 did not change appreciably 3 (SPy = 4-mercaptopyridine) reported previosuly. 27 Both the Au 11 unit of 1 and the Au 11 core of 2 take the well-known tetra-capped centered chair motif, 1,3 although close inspection showed that they are slightly distorted ( Figure S4 of the supplementary material). Three p-MBA ligands are directly coordinated to Au 11 in both 1 and 2 without forming the semi-ring motif -SR-(Au-SR-) n (n = 1-3) conventionally found in the thiolateprotected Au clusters.…”

mentioning

confidence: 99%