The Au25(pMBA)17Diglyme Cluster

A modification of Au25(pMBA)18 that incorporates one diglyme ligand as a direct synthetic product is reported. Notably the expected statistical production of clusters containing other ligand stoichiometries is not observed. This Au25(pMBA)17diglyme product is characterized by electrospray ionization mass spectrometry (ESI-MS) and optical spectroscopy. Thiolate for thiolate ligand exchange proceeds on this cluster, whereas thiolate for diglyme ligand exchange does not.

Post-Synthesis Modification of Photoluminescent and Electrochemiluminescent Au Nanoclusters with Dopamine

Here, we report a post-synthesis functionalization of the shell of Au nanoclusters (NCs) synthesized using glutathione as a thiolate ligand. The as-synthesized Au NCs are subjected to the post-synthesis functionalization via amidic coupling of dopamine on the cluster shell to tailor photoluminescence (PL) and electrochemiluminescence (ECL) features of the Au NCs. Because the NCs’ PL at ca. 610 nm is primarily ascribed to the Au(I)-thiolate (SG) motifs on the cluster shell of the NCs, the post-synthesis functionalization of the cluster shell enhanced the PL intensity of the Au NCs via rigidification of the cluster shell. In contrast to the PL enhancement, the post-synthesis modification of the cluster shell does not enhance the near-infrared (NIR) ECL of the NCs because the NIR ECL at ca. 800 nm is ascribed to the Au(0)-SG motifs in the metallic core of the NCs.

Control of single-ligand chemistry on thiolated Au25 nanoclusters

Diverse methods have been developed to tailor the number of metal atoms in metal nanoclusters, but control of surface ligand number at a given cluster size is rare. Here we demonstrate that reversible addition and elimination of a single surface thiolate ligand (-SR) on gold nanoclusters can be realized, opening the door to precision ligand engineering on atomically precise nanoclusters. We find that oxidative etching of [Au25SR18]− nanoclusters adds an excess thiolate ligand and generates a new species, [Au25SR19]0. The addition reaction can be reversed by CO reduction of [Au25SR19]0, leading back to [Au25SR18]− and eliminating precisely one surface ligand. Intriguingly, we show that the ligand shell of Au25 nanoclusters becomes more fragile and rigid after ligand addition. This reversible addition/elimination reaction of a single surface ligand on gold nanoclusters shows potential to precisely control the number of surface ligands and to explore new ligand space at each nuclearity.

[(Z)-N-(3-Fluorophenyl)-O-methylthiocarbamato-κS](triphenylphosphane-κP)gold(I): crystal structure, Hirshfeld surface analysis and computational study

The title phosphanegold(I) thiolate, C26H22AuFNOPS or [Au(C8H7FNOS)(C18H15P)], has the AuI centre coordinated by phosphane-P [2.2494 (8) Å] and thiolate-S [2.3007 (8) Å] atoms to define a close to linear geometry [P—Au—S = 176.10 (3)°]. The thiolate ligand is orientated so that the methoxy-O atom is directed towards the Au atom, forming an Au...O close contact of 2.986 (2) Å. In the crystal, a variety of intermolecular contacts are discerned with fluorobenzene-C—H...O(methoxy) and phenyl-C—H...F interactions leading to dimeric aggregates. These are assembled into a three-dimensional architecture by phenyl-C—H...S(thiolate) and phenyl-C—H...π(fluorobenzene, phenyl) interactions. Accordingly, the analysis of the calculated Hirshfeld surface shows 30.8% of all contacts are of the type C...H/H...C but this is less than the H...H contacts, at 44.9%. Other significant contributions to the surface come from H...F/F...H [8.1%], H...S/S...H [6.9%] and H...O/O...H [3.2%] contacts. Two major stabilization energies have contributions from the phenyl-C—H...π(fluorobenzene) and fluorobenzene-C—H...C(imine) interactions (−37.2 kcal mol−1), and from the fluorobenzene-C—H...F and phenyl-C—H...O interactions (−34.9 kcal mol−1), the latter leading to the dimeric aggregate.

Nickel-Catalyzed Negishi-Type Arylation of Trialkylsulfonium Salts

Negishi-type arylation of trialkylsulfonium salts with arylzinc reagents has been accomplished under nickel catalysis. The use of cyclohexanethiol as an additional ligand was found to be particularly important to promote C–S cleavage. The present reaction accommodates one-pot arylation of dialkyl sulfides by combining with S-methylation with MeOTf. Mechanistic experiments suggest that C–S cleavage would proceed via single-electron transfer (SET) to generate the most stable carbon-centered radical and that the thiolate ligand would promote the C–S cleavage and radical recombination step.

Synthesis and properties of an Au6 cluster supported by a mixed N-heterocyclic carbene–thiolate ligand

The preparation of a novel Au6 cluster bearing a bidentate mixed carbene–thiolate ligand is presented.

Effect of thiolate-ligand passivation on the electronic structure and optical absorption properties of ultrathin one and two-dimensional gold nanocrystals

Gold nanomaterials, including one-dimensional (1D) gold nanorods (AuNRs) and nanowires (AuNWs) and two-dimensional (2D) gold nanoprisms with a large surface area and stability, have attracted widespread research interest due to their wide potential applications.

First member of an appealing class of cyclometalated 1,3-di-(2-pyridyl)benzene platinum(ii) complexes for solution-processable OLEDs

A novel highly luminescent N^C^N Pt(ii) complex with a thiolate ligand allows fabrication of efficient processable solution-OLEDs with a tuneable color.

(2-{[2-(Dimethylamino)ethyl]iminomethyl}benzenethiolato-κ3 N,N′,S)(4-methoxybenzenethiolato-κS)nickel(II)

In the title compound, [Ni(C11H15N2S)(C7H7OS)] or [Ni(NNImS)(4-OCH3PhS)] (NNImS = 2-{[2-(dimethylamino)ethyl]iminomethyl}benzenethiolato), the NiII cation is coordinated by a tridentate NNImS ligand and a monodentate thiolate ligand giving an N2S2 coordination set defining an almost square-planar environment. The Ni—Namine bond in the coordination plane is approximately 0.1 Å longer than the Ni—Nimine bond.