Gold-carbon Bond Research Articles

Impact of Graphene Oxide on SERS Enhancement of Arylated Gold Nanospheres: Mechanistic Insight.

The performance of gold nanospheres as substrates for surface-enhanced Raman spectroscopy (SERS) investigation has been compromised by their low adsorption efficiency, high colloidal dispersibility, and diminishing hot spots. However, gold nanosphere substrates modified using aryldiazonium gold(III) chemistry via durable gold-carbon bonds are promising for SERS enhancement due to their controlled organic layer density. In this study, arylated gold nanospheres AuNSs-COOH have shown SERS enhancement when incorporated into graphene oxide (GO) to form nanocomposites (NCs) labeled AuNSs-COOH/GO (AuNCs). Our investigation using X-ray photoelectron spectroscopy (XPS) surface analysis showed that the gold-aryl nanospheres reached their maximum SERS enhancement with an optimal coating. The evaluation included the Au 4f chemical environment and compact graphitic layers for the SERS substrate optimization. The fabricated AuNC substrates demonstrated superior efficiency and reproducibility. A broad linear range of 10-3-10-7 M 4-nitrophenol detection was obtained with exceptional repeatability, as evidenced by the relative standard deviation (RSD) of 9.32%. A detailed investigation of the energy profiles, particularly the valence band maximum (VBM) and band gap values of the substrate and analyte, depicted the electromagnetic (EM) and charge-transfer-induced enhancement and the role of GO inclusion in substrate efficiency in SERS enhancement mechanisms. The finite-difference time domain (FDTD) simulation results revealed that AuNCs incorporated with graphitic nanostructures exhibited the most substantial SERS effect through an EM field enhancement mechanism. This study demonstrated significant SERS enhancement using gold-aryl nanospheres when modified with GO, in contrast to the typical reliance on anisotropic nanostructures.

Electronic transport through single-molecule oligophenyl-diethynyl junctions with direct gold-carbon bonds formed at low temperature.

We report on the first systematic transport study of alkynyl-ended oligophenyl-diethynyl (OPA) single-molecule junctions with direct Au–C anchoring scheme at low temperature using the mechanically controlled break junction technique. Through quantitative statistical analysis of opening traces, conductance histograms and density functional theory studies, we identified different types of junctions, classified by their conductance and stretching behavior, for OPA molecules between Au electrodes with two to four phenyl rings. We performed inelastic electron tunneling spectroscopy and observed the excitation of Au–C vibrational modes confirming the existence of Au–C bonds at low temperature and compared the stability of molecule junctions upon mechanical stretching. Our findings reveal the huge potential for future functional molecule transport studies at low temperature using alkynyl endgroups.

Migratory Insertion of Carbenes into Au(III)-C Bonds.

Migratory insertion of carbon-based species into transition-metal–carbon bonds is a mechanistic manifold of vast significance: it underlies the Fischer–Tropsch process, Mizoroki–Heck reaction, Ziegler–Natta and analogous late-transition-metal-catalyzed olefin polymerizations, and a number of carbonylative methods for the synthesis of ketones and esters, among others. Although this type of reactivity is well-precedented for most transition metals, gold constitutes a notable exception, with virtually no well-characterized examples known to date. Yet, the complementary reactivity of gold to numerous other transition metals would offer new synthetic opportunities for migratory insertion of carbon-based species into gold–carbon bonds. Here we report the discovery of well-defined Au(III) complexes that participate in rapid migratory insertion of carbenes derived from silyl- or carbonyl-stabilized diazoalkanes into Au–C bonds at temperatures ≥ −40 °C. Through a combined theoretical and experimental approach, key kinetic, thermodynamic, and structural details of this reaction manifold were elucidated. This study paves the way for homogeneous gold-catalyzed processes incorporating carbene migratory insertion steps.

Facile synthesis of stable, water soluble, dendron-coated gold nanoparticles.

Upon reduction with sodium borohydride, diazonium tetrachloroaurate salts of triazine dendrons yield dendron-coated gold nanoparticles connected by a gold-carbon bond. These robust nanoparticles are stable in water and toluene solutions for longer than one year and present surface groups that can be reacted to change surface chemistry and manipulate solubility. Molecular modeling was used to provide insight on the hydration of the nanoparticles and their observed solubilties.

Cationic Gold(III) Alkyl Complexes: Generation, Trapping, and Insertion of Norbornene

AbstractMigratory insertion of alkenes into gold–carbon bonds, a fundamental yet unprecedented organometallic transformation, has been investigated from a discrete (P,C) cyclometalated gold(III) dimethyl complex. Methide abstraction by B(C6F5)3 is shown to generate a highly reactive cationic AuIII complex that evolves spontaneously by C6F5 transfer from boron. In the presence of norbornene, migratory insertion into the AuC bond proceeds readily. The resulting norbornyl complex is efficiently trapped with pyridines or chloride to give stable four‐coordinate adducts.

Cationic gold(III) alkyl complexes: generation, trapping, and insertion of norbornene.

Migratory insertion of alkenes into gold-carbon bonds, a fundamental yet unprecedented organometallic transformation, has been investigated from a discrete (P,C) cyclometalated gold(III) dimethyl complex. Methide abstraction by B(C6F5)3 is shown to generate a highly reactive cationic Au(III) complex that evolves spontaneously by C6F5 transfer from boron. In the presence of norbornene, migratory insertion into the Au-C bond proceeds readily. The resulting norbornyl complex is efficiently trapped with pyridines or chloride to give stable four-coordinate adducts.

Trimethyltin-mediated covalent gold-carbon bond formation.

We study the formation of covalent gold-carbon bonds in benzyltrimethylstannane (C10H16Sn) deposited on Au in ultra-high-vacuum conditions. Through X-ray photoemission spectroscopy and X-ray absorption measurements, we find that the molecule fragments at the Sn-benzyl bond when exposed to Au surfaces at temperatures as low as -110 °C. The resulting benzyl species is stabilized by the presence of Au(111) but only forms covalent Au-C bonds on more reactive Au surfaces like Au(110). We also present spectroscopic proof for the existence of an electronic "gateway" state localized on the Au-C bond that is responsible for its unique electronic properties. Finally, we use DFT-based nudged elastic band calculations to elucidate the crucial role played by the under-coordinated Au surface in the formation of Au-C bonds.

Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold.

Since the first report of thiol-based self-assembled monolayers (SAMs) 30 years ago, these structures have been examined in a huge variety of applications. The oxidative and thermal instabilities of these systems are widely known, however, and are an impediment to their widespread commercial use. Here, we describe the generation of N-heterocyclic carbene (NHC)-based SAMs on gold that demonstrate considerably greater resistance to heat and chemical reagents than the thiol-based counterparts. This increased stability is related to the increased strength of the gold-carbon bond relative to that of a gold-sulfur bond, and to a different mode of bonding in the case of the carbene ligand. Once bound to gold, NHCs are not displaced by thiols or thioethers, and are stable to high temperatures, boiling water, organic solvents, pH extremes, electrochemical cycling above 0V and 1% hydrogen peroxide. In particular, benzimidazole-derived carbenes provide films with the highest stabilities and evidence of short-range molecular ordering. Chemical derivatization can be employed to adjust the surface properties of NHC-based SAMs.

Tuning Rectification in Single-Molecular Diodes

We demonstrate a new method of achieving rectification in single molecule devices using the high-bias properties of gold-carbon bonds. Our design for molecular rectifiers uses a symmetric, conjugated molecular backbone with a single methylsulfide group linking one end to a gold electrode and a covalent gold-carbon bond at the other end. The gold-carbon bond results in a hybrid gold-molecule "gateway" state pinned close to the Fermi level of one electrode. Through nonequilibrium transport calculations, we show that the energy of this state shifts drastically with applied bias, resulting in rectification at surprisingly low voltages. We use this concept to design and synthesize a family of diodes and demonstrate through single-molecule current-voltage measurements that the rectification ratio can be predictably and efficiently tuned. This result constitutes the first experimental demonstration of a rationally tunable system of single-molecule rectifiers. More generally, the results demonstrate that the high-bias properties of "gateway" states can be used to provide additional functionality to molecular electronic systems.

Probing the nature of gold–carbon bonding in gold–alkynyl complexes

Homogeneous catalysis by gold involves organogold complexes as precatalysts and reaction intermediates. Fundamental knowledge of the gold–carbon bonding is critical to understanding the catalytic mechanisms. However, limited spectroscopic information is available about organogolds that are relevant to gold catalysts. Here we report an investigation of the gold–carbon bonding in gold(I)–alkynyl complexes using photoelectron spectroscopy and theoretical calculations. We find that the gold–carbon bond in the ClAu–CCH− complex represents one of the strongest gold–ligand bonds—even stronger than the known gold–carbon multiple bonds, revealing an inverse correlation between bond strength and bond order. The gold–carbon bond in LAuCCH− is found to depend on the ancillary ligands and becomes stronger for more electronegative ligands. The strong gold–carbon bond underlies the catalytic aptness of gold complexes for the facile formation of terminal alkynyl–gold intermediates and activation of the carbon–carbon triple bond.

Arylgold(I) Complexes from Base-Assisted Transmetalation: Structures, NMR Properties, and Density-Functional Theory Calculations

The synthesis of gold(I) complexes of the type LAuR (L = PCy(3), IPr; R = aryl; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) starting from LAuX (X = Br, OAc) and boronic acids in the presence of Cs(2)CO(3) has been investigated. The reactions proceed smoothly in good to excellent yields over the course of 24-48 h in isopropyl alcohol at 50-55 °C. The aryl groups include a variety of functionalities and steric bulk, and in two cases, are heterocyclic. All of the products have been characterized by multinuclear NMR spectroscopy and elemental analysis and most by X-ray crystallography. This work affirms that, almost without exception, base-assisted auration is a useful and reliable way to form gold-carbon bonds.

A Stable Acyclic Ligand Equivalent of an Unstable 1,3‐Dithiol‐5‐ylidene

A Stable Acyclic Ligand Equivalent of an Unstable 1,3‐Dithiol‐5‐ylidene

First structurally confirmed example of the formation of a gold(iii) carbon bond via transmetallation with a boroxine

Cyclometallated gold(III) complexes containing functionalised (2-dimethylaminomethyl)phenyl ligands have been prepared by transmetallation from boroxines to sodium tetrachloroaurate.

Synthesis and Characterization of Gold‐Nanoparticle‐Cored Dendrimers Stabilized by Metal–Carbon Bonds

Synthesis and characterization of gold-nanoparticle-cored dendrimers (NCDs), in which the dendrons are attached to the gold core through gold-carbon bonds, are described. Synthesis of these materials involved the simultaneous reduction of HAuCl(4) and a Fréchet-type dendron with a diazonium group at the focal point, all in an organic solvent such as toluene. These materials possess a nanometer-sized gold core surrounded by a shell of polyaryl ether dendrons, which are connected radially to the core. The NCDs were characterized by TEM, thermogravimetric analysis (TGA), and IR, UV, and NMR spectroscopic techniques. Average particle diameter of the NCDs ranged from 4.7 to 5.5 nm for the different generations. All NCDs exhibit the characteristic plasmon absorption of gold nanoparticles at 520 nm. Average numbers of dendrons per NCD in AuG(n) were calculated using results from TGA and TEM studies. Multiple layering of the dendrons is proposed as a possible reason for the high dendron/NCD value.

Carbene or cation?

The exact nature of the gold–carbon bond formed during homogeneous gold catalysis has recently attracted a lot of interest and is somewhat controversial. Now a study of the bonding and trends in reactivity of various gold complexes offers new insights into whether such structures can be defined as gold-stabilized cations or gold carbenes.

Reactions of Cationic Gold(I) with Allenoates: Synthesis of Stable Organogold(I) Complexes and Mechanistic Investigations on Gold‐Catalyzed Cyclizations

The reaction of allenoates with cationic gold(I)-generated in situ from a phosphine gold chloride and a silver salt-formed unusual, room temperature stable vinyl gold(I) lactones under very mild conditions. The scope and limitations for the synthesis of this novel organogold complex was investigated. DFT calculations on the highest occupied molecular orbitals (HOMOs) of allenoates and the natural bond orbital (NBO) charge densities provided an explanation for the limitations. A plausible mechanism for its formation was proposed based on in situ (1)H and (31)P NMR spectroscopic analyses. Controlled experiments for the cleavage of the gold-carbon bond by electrophiles indicated that this vinyl gold(I) complex is the likely intermediate in the gold-catalyzed reaction of carbon-carbon multiple bonds.

The effect of stretching thiyl– and ethynyl–Au molecular junctions

We perform density functional theory (DFT) calculations of the stretching ofAu(111)–X–Au(111) molecular junctions where X is either a thiyl or ethynyl biradical. Theequilibrium geometries for the radicals adsorbing on the surface are first calculated and theradicals then placed in the junction geometry. The unit cell is stepwise increased in lengthand the geometry relaxed at each step. When stretching the ethynyl junction, a single goldatom is detached from the rest of the surface and the gold–carbon bond does not break. Incontrast, the gold–sulfur bond in the thiyl junction breaks without detaching anygold atoms. This behaviour can be attributed to the enhanced strength of theAu–C interaction over the Au–S interaction. In both junctions the conductancecalculated using the non-equilibrium Green’s function formalism (NEGF) decreasesas the junction is stretched. After breakage of the Au–S bond, the thiyl radicalcontains an unpaired electron on the sulfur atom and the system is in a spindoublet state. Transmission spectra were calculated for the spin-unpolarized caseonly; evaluation of the spin-polarized density of states suggests that an enhancedconductance for electrons of one spin type may be observed after the Au–S bond isbroken.

Synthesis, Structural Characterisation and Reactions of Some Vinylgold(I) Phosphane Complexes

AbstractA series of vinylgold(I) complexes [Au(CR=CHR)L] (R = H, Me; L = PPh3, PPh2Me, PPhMe2) were prepared from the reaction of the Grignard reagents [MgBr(CR=CHR)] (R = H, Me) with the gold(I) phosphane complexes [AuCl(L)] (L = PPh3, PPh2Me, PPhMe2) at low temperature. The complexes were characterised by various spectroscopic techniques and, in the case of [Au(CMe=CHMe)(PPh3)], by a single‐crystal X‐ray structure determination. The gold–carbon bonds of these vinylgold(I) complexes are easily cleaved by acids and, in the presence of potassium permanganate, by species containing acidic protons. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Aromatic and Antiaromatic Gold(III) Hexaphyrins with Multiple Gold−Carbon Bonds

Au(III) metalation of hexakis(pentafluorophenyl) [26]hexaphyrin led to formation of aromatic mono-Au(III) hexaphyrin and bis-Au(III) hexaphyrin, in which the inner pyrrolic beta-protons are activated to form gold-carbon bonds, hence accommodating Au(III) ion with a NNCC core in a square planar manner. Two-electron reductions of these complexes with NaBH4 provided the corresponding [28]hexaphyrin complexes which exhibit distinct paratropic ring currents.

Soldering of Carbon Nanotube Bridges using Electron Beam Deposited Gold

AbstractWe have formed suspended bridges of carbon nanotubes between microcantilevers using electron beam dissociation of metal-organic vapours. By electron beam exposure of a surface in the presence of gold-carbon molecules emitted inside an environmental scanning electron microscope, we are able to form tips and other freestanding nanostructures of high metallic content. Suspended bridges made entirely of this material exhibit resistances less than 50 times that of pure gold, and consist of dense metallic cores surrounded by a crust of nanoparticles. We used standard microfabrication techniques to produce silicon chips with multiple microcantilevers extending over the edge. Individual multiwalled carbon nanotubes grown catalyticcally by chemical vapour deposition, were positioned across two cantilevers using in-situ nanomanipulation tools. Drawing a cross-shaped gold-carbon bond on each end of the carbon nanotube consistently resulted in electrical contact with resistances in the range 1-90 Ω and linear current-voltage characteristics. We found that soldering bonds having a line width down to 10-15 nm form connections and last for days in ambient conditions.