The atomic metal core structures of the subnanometer clusters Au13[PPh3]4[S(CH2)11CH3]2Cl2 (1) and Au13[PPh3]4[S(CH2)11CH3]4 (2) were characterized using advanced methods of electron microscopy and X-ray absorption spectroscopy. The number of gold atoms in the cores of these two clusters was determined quantitatively using high-angle annular dark field scanning transmission electron microscopy....

Understanding the effect of interfacial interactions between protection motifs and gold cores on stabilities thiolate-protected nanoclusters is still a challenging task. Based analyses 95 experimentally crystallized theoretically predicted nanoclusters, we present ring model to offer deeper insight into for this class nanoclusters. In model, all can be generically viewed as fusion or interlocki...

The reactions of the tetraphosphine ligand DAB-G0-(PPh2)4 (DAB = 1,4-diaminobutane; G0 = Generation 0) or the octaphosphine ligand DAB-G1-(PPh2)8 (G1 = Generation 1) with the gold precursor [AuCl(tht)] (tht =tetrahydrothiophene) and the corresponding 4-substituted benzenethiolate lead to the (phosphine)gold(I) thiolate complexes [Au4(S-C6H4-X)4[(DAB-G0-(PPh2)4]] (X = F (11), MeO (12), Me (13) a...

We report a new activation method and insight into the catalytic behavior of a CeO2-supported, atomically precise Au144(SR)60 nanocluster catalyst (where thiolate -SR = -SCH2CH2Ph) for CO oxidation. An important finding is that the activation of the catalyst is closely related to the production of active oxygen species on CeO2, rather than ligand removal of the Au144(SR)60 clusters. A mild O2 p...

The synthesis of stable and isolable iridium nanoparticles with an average core size of ∼1.2 ± 0.3 nm was achieved by employing sodium S-dodecylthiosulfate as a ligand precursor during the modified Brust-Schiffrin reaction. Transmission electron microscopy (TEM) of the isolated Ir nanoparticles revealed a high degree of monodispersity. Further characterizations with 1H NMR, FT-IR, UV-vis spectr...

Reaction of [Pt(L)(μ-Cl)](2) (L = ppy (2-phenylpyridine) or bzq (benzo[h]quinoline)) with 2-mercaptobenzoxazole (NOSH) and NaOAc in THF at r.t. yields the dinuclear Pt(II) d(8)-d(8) complexes [Pt(2)L(2)(μ-NOS-κN,S)(2)] (L = ppy, 1; L = bzq, 2) and the Pt(III) d(7)-d(7) complexes [Pt(2)(ppy)(2)(μ-NOS-κN,S)(2)(NOS-κS)(2)] (L = ppy, 3; L = bzq, 4) in one pot. The C,N-cyclometalated ligand is chela...

Synthesized thiolate boronic acid was found to complex with both a polysaccharide (dextran) and a monosaccharide (glucose) with similar affinities but displayed more affinity with dextran than with glucose when capped as a ligand on silver nanoparticle. Coupling on multiple sites of dextran, the silver particles were aggregated. The aggregated particles displayed a decrease of absorbance at 397...

A new monoanionic dithiolene ligand is found in Tp*MoO(S(2)BMOQO). A combination of X-ray crystallography, electronic absorption spectroscopy, resonance Raman spectroscopy, and bonding calculations reveal that the monoanionic dithiolene ligand possesses considerable thiolate-thione character resulting from an admixture of an intraligand charge transfer excited state into the ground state wave f...

The redox chemistry of mononuclear and dinuclear gold(I) phosphine arylthiolate complexes was recently investigated by using electrochemical, chemical, and photochemical techniques. We now report the redox chemistry of dinuclear gold(I) phosphine complexes containing aliphatic dithiolate ligands. These molecules differ from previously studied gold(I) phosphine thiolate complexes in that they ar...

Staple motifs in the form of -RS(AuSR)x- (x = 1, 2, 3, etc.) are the most common structural feature at the interface of the thiolate-protected gold nanoclusters, Aun(SR)m. However, the recently solved structure of Au92(SR)44, in which the facets of the Au84 core are protected mainly by the bridging thiolates, challenges the staple hypothesis. Herein, we explore the surface sensitivity of the th...