All-Hydrocarbon-Ligated Superatomic Gold/Aluminum Clusters.

Key strategies in cluster synthesis include the use of modulating agents (e.g., coordinating additives). We studied the influence of various phosphines exhibiting different steric and electronic properties on the reduction of the Au(I) precursor to Au(0) clusters. We report a synthesis of the bimetallic clusters [Au6(AlCp*)6] = [Au6Al6](Cp*)6 (1) and [HAu7(AlCp*)6] = [HAu7Al6](Cp*)6 (2) (Cp* = pentamethylcyclopentadiene) using Au(I) precursors and AlCp*. The cluster [Au2(AlCp*)5] = [Au2Al5](Cp*)5 (3) was isolated and identified as an intermediate species in the reactions to 1 and 2. The processes of cluster growth and degradation were investigated by in situ 1H NMR and LIFDI-MS techniques. The structures of 1 and 2 were established by DFT geometry optimization. These octahedral clusters can both be described as closed-shell 18-electron superatoms.

Metal-Metal Bonding in Late Transition-Metal [M2L5] Complexes: Exploring the Limits of the Isolobal Analogy between the CO and AlCp* Ligands.

Late dinuclear transition-metal (especially group 10 and 11) homoleptic carbonyl complexes are elusive species and have so far not been isolated. A typical example is the 30-electron species [Ni2(CO)5], the structure and bonding of which is still debated. We show that, by using the AlCp* ligand (isolobal to CO), it is possible to isolate and fully characterize [Ni2(AlCp*)5] (1), which inspired us to revisit by DFT calculations, the bonding situation within [Ni2L5] (L = CO, AlCp*) and other isoelectronic species. The short Ni-Ni X-ray distance in 1 (2.270 Å) should not be attributed to the existence of a typical localized triple-bond between the metals, but rather to a strong through-bond interaction involving the three bridging ligands via their donating lone pairs and accepting π* orbitals. In contrast, in the isostructural 32-electron [Au2(AlCp*)5] (2) cluster an orbital with M-M antibonding and Al...Al bonding character is occupied, which is in accordance with the particularly long Au-Au distance (3.856 Å) and rather short Al...Al contacts between the bridging ligands (2.843 Å). This work shows that, unlike late transition-metal [M2(CO)x] species, stable [M2(AlCp*)x] complexes can be isolated, owing to the subtle differences between CO and AlCp*. We propose a similar approach for rationalizing the bonding in the emblematic 34 electron species [Fe2(CO)9].

Intermetallic phases meet intermetalloid clusters.

In this article intermetalloid clusters of Cu-Zn, Cu-AI, Cu-Sn, and Cu-Pb are discussed. Intermetallic compounds based on these metal combinations are of the Hume-Rothery type with well-defined structures related to the valence electron count of the involved metals. Many Zintl-type and molecular clusters with these metals are known with remarkable structural parallels to the respective solid-state phases. On several examples, this article discusses intermetalloid clusters in terms of their metal core structures and relates them to structural principles in intermetallic solid-state phases. Also the syntheses of such clusters are addressed. Zintl-type and molecular clusters are most generally accessible from organometallic precursor complexes with redox processes between the different metals as an underlying synthesis concept.

Contrasting Structure and Bonding of a Copper-Rich and a Zinc-Rich Intermetalloid Cu/Zn Cluster.

Reaction of the Cu(I) sources, [Cu5](Mes)5 and [(iDipp)CuOtBu] (Mes = mesityl; iDipp = 1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene) with the Zn(I) complex [Zn2](Cp*)2 leads to a mixture of intermetallic Cu/Zn clusters with a distribution of species that is dependent on the stoichiometric ratio of the reactants, the reaction time, as well as the temperature. Systematic and careful investigation of the product mixtures rendered the isolation of two new clusters possible, i.e., the Zn-rich, red cluster 1, [CuZn10](Cp*)7 = [Cu(ZnZnCp*)3(ZnCp*)4], as well as the Cu-rich, dark-green cluster 2 [Cu10Zn2](Mes)6(Cp*)2. Structure and bonding of these two species was rationalized with the help of density functional theory calculations. Whereas 1 can be viewed as an 18-electron Cu center coordinated to four ZnCp* and three ZnZnCp* one-electron ligands (with some interligand bonding interaction), compound 2 is better to be described as a six-electron superatom cluster. This unusual electron count is associated with a prolate distortion from a spherical superatom structure. This unexpected situation is likely to be associated with the ZnCp* capping units that offer the possibility to strongly bind to the top and the bottom of the cluster in addition to the bridging mesityl ligands stabilizing the Cu core of the cluster.

Remarkably Intricate Raman Spectra of Platinum(II)-Ligand Skeletal Modes in Diamminedihalido Complexes.

More than 100 calculations of vibrational frequencies for cis-[Pt(NH3)2X2] (X = Cl-, Br-) and trans-[Pt(NH3)2Cl2] have been published over the past 25 years. The high-quality Raman spectra presented here have sufficient resolution in the crucial region of metal-ligand modes to permit an assessment of frequency calculations. The peaks for symmetric and antisymmetric Pt-Cl stretching modes νs and νa are resolved in the 312-333 cm-1 region. Frequency variations due to 35Cl and 37Cl isotopes are shown to be comparable in size to the differences between νs and νa. Peaks corresponding to the two Pt-Br stretching frequencies are observed at 213 and 218 cm-1 and Pt-N stretching frequencies for all compounds between 485 and 540 cm-1. The crystal structures of trans-[Pt(NH3)2Cl2] and cis-[Pt(NH3)2Br2] at 300 and 120 K are reported and complement the variable-temperature vibrational frequencies.

Molecularly linked 3D plasmonic nanoparticle core/satellite assemblies: SERS nanotags with single-particle Raman sensitivity.

A fast, generic, and suspension-based route to highly SERS-active assemblies of noble metal nanoparticles (Au, Ag) with small core-satellite gaps and single-particle Raman sensitivity is presented. Rationally designed, heterobifunctional Raman reporters serve as molecular linkers for electrostatic conjugation of the small satellites to the large core.

Assignment of individual structures from intermetalloid nickel gallium cluster ensembles.

Poorly selective mixed-metal cluster synthesis and separation yield reaction solutions of inseparable intermetalloid cluster mixtures, which are often discarded. High-resolution mass spectrometry, however, can provide precise compositional data of such product mixtures. Structure assignments can be achieved by advanced computational screening and consideration of the complete structural space. Here, we experimentally verify structure and composition of a whole cluster ensemble by combining a set of spectroscopic techniques. Our study case are the very similar nickel/gallium clusters of M12, M13 and M14 core composition Ni6+xGa6+y (x + y ≤ 2). The rationalization of structure, bonding and reactivity is built upon the organometallic superatom cluster [Ni6Ga6](Cp*)6 = [Ga6](NiCp*)6 (1; Cp* = C5Me5). The structural conclusions are validated by reactivity tests using carbon monoxide, which selectively binds to Ni sites, whereas (triisopropylsilyl)acetylene selectively binds to Ga sites.

Microspectroscopic SERS detection of interleukin-6 with rationally designed gold/silver nanoshells.

Rationally designed gold/silver nanoshells (Au/Ag-NS) with plasmon resonances optimized for red laser excitation in order to minimize autofluorescence from clinical samples exhibit scattering cross-sections, which are ca. one order of magnitude larger compared with solid quasi-spherical gold nanoparticles (Au-NPs) of the same size. Hydrophilic stabilization and sterical accessibility for subsequent bioconjugation of Au/Ag-NS is achieved by coating their surface with a self-assembled monolayer (SAM) of rationally designed Raman reporter molecules comprising terminal mono- and tri-ethylene glycol (EG) spacers, respectively. The stability of the hydrophilically stabilized metal colloid was tested under different conditions. In contrast to metal colloids coated with a SAM without terminal EG spacers, the hydrophilically stabilized SERS particles do not aggregate under physiologically relevant conditions, i.e., buffer solutions with high ionic strength. Using these rationally designed SERS particles in conjunction with a microspectroscopic acquisition scheme, a sandwich immunoassay for the sensitive detection of interleukin-6 (IL-6) was developed. Several control experiments demonstrate the high specificity of the assay towards IL-6, with a lowest detectable concentration of ca. 1 pg mL(-1). The signal strength of the Au/Ag-NS is at least one order of magnitude higher compared with hydrophilically stabilized, non-aggregated solid quasi-spherical Au-NPs of the same size.

Photochemically generated reactive sites at ruthenium/gallium complexes: catalysis vs. cluster growth.

Irradiation of [Ru(GaCp*)3(SiEt3)H3] (1) at 350 nm induces reductive elimination of dihydrogen and triethylsilane and generates unsaturated Ru/Ga species. This photochemically induced cascading reductive elimination processes generate the reactive intermediate [Ru(GaCp*)3], which can be trapped by diphosphine coordination to yield the stable complex [(dppe)Ru(GaCp*)3] (4). The photochemically generated RuGa3 species is catalytically active in the hydrogenation of alkynes, which is further investigated by 1H NMR and mass spectrometry. Formation of intermetallic Ru/Ga clusters is observed as a competing and for the catalytic activity of the species limiting side reaction.

Immuno-surface-enhanced coherent anti-stokes Raman scattering microscopy: immunohistochemistry with target-specific metallic nanoprobes and nonlinear Raman microscopy.

Immunohistochemistry (IHC) is one of the most widely used staining techniques for diagnostic purposes. The selective localization of target proteins in tissue specimens by conventional IHC is achieved with dye- or enzyme-labeled antibodies in combination with light microscopy. In this contribution, we demonstrate the proof-of-principle for IHC based on surface-enhanced coherent Raman scattering for contrast generation. Specifically, antibody-labeled metallic nanoshells in conjunction with surface-enhanced coherent anti-Stokes Raman scattering (SECARS) microscopy are employed for the selective, sensitive, and rapid localization of the basal cell protein p63 in normal prostate tissue. Negative control experiments were performed in order to confirm the selective binding of the target-specific metal nanoprobes and to disentangle the role of plasmonic (metal) and molecular (Raman reporter) resonances in this plasmon-assisted four-wave mixing technique.

Fast and cost-effective purification of gold nanoparticles in the 20-250 nm size range by continuous density gradient centrifugation.

A multilayer quasi-continuous density gradient centrifugation method for separating 20-250 nm metal colloids with high size resolution while maintaining particle stability is presented. Colloidal mixtures containing monodisperse gold nanospheres and clusters thereof, in particular, gold dimers, are purified with yields up to 94%. The rapid method uses standard laboratory equipment.

3D self-assembled plasmonic superstructures of gold nanospheres: synthesis and characterization at the single-particle level.

The synthesis of 3D self-assembled plasmonic superstructures of gold nanospheres as well as the characterization of their structural and optical properties at the single-particle level is presented. This experimental work is complemented by FEM (finite element method) simulations of elastic scattering spectra and the spatial |E|(4) distribution for establishing structure-activity correlations in these complex 3D nanoclusters.

Enabling LIFDI-MS measurements of highly air sensitive organometallic compounds: a combined MS/glovebox technique.

A new setup combining a ThermoFisher Exactive Plus Orbitrap Mass Spectrometer with a liquid injection field desorption ionization (LIFDI) source directly connected to an inert atmosphere glovebox is presented. The described setup allows for the analysis of very air- and moisture sensitive samples. Furthermore, the soft nature of LIFDI ionization gives access to the molecular ions of fragile molecules. This new setup is therefore especially useful for sensitive organometallic complexes. The functionality of the new setup is tested against [(Cp)2TiCl]˙, which is known for its notorious sensitivity to air and moisture. Its drastic colour change from green to orange upon exposure to air further supports the easy detection of traces of oxygen during the experiment. In addition, we applied this setup to the mass spectrometric analysis of the qualitative composition of a Cu/Al cluster mixture, which is not accessible by other analytical methods.

Exploring Cu/Al cluster growth and reactivity: from embryonic building blocks to intermetalloid, open-shell superatoms.

Cluster growth reactions in the system [Cu5](Mes)5 + [Al4](Cp*)4 (Mes = mesitylene, Cp* = pentamethylcyclopentadiene) were explored and monitored by in situ LIFDI-MS and 1H-NMR. Feedback into experimental design allowed for an informed choice and precise adjustment of reaction conditions and led to isolation of the intermetallic cluster [Cu4Al4](Cp*)5(Mes) (1). Cluster 1 reacts with excess 3-hexyne to yield the triangular cluster [Cu2Al](Cp*)3 (2). The two embryonic [Cu4Al4](Cp*)5(Mes) and [Cu2Al](Cp*)3 clusters 1 and 2, respectively, were shown to be intermediates in the formation of an inseparable composite of the closely related clusters [Cu7Al6](Cp*)6 (3), [HCu7Al6](Cp*)6 (3H) and [Cu8Al6](Cp*)6 (4), which just differ by one Cu core atom. The radical nature of the open-shell superatomic [Cu7Al6](Cp*)6 cluster 3 is reflected in its reactivity towards addition of one Cu core atom leading to the closed shell superatom [Cu8Al6](Cp*)6 (4), and as well by its ability to undergo σ(C-H) and σ(Si-H) activation reactions of C6H5CH3 (toluene) and (TMS)3SiH (TMS = tris(trimethylsilyl)).

SERS labels for red laser excitation: silica-encapsulated SAMs on tunable gold/silver nanoshells.

In a glass house: Silica-encapsulated self-assembled monolayers (SAMs) on tunable gold/silver nanoshells were used as labels for surface-enhanced Raman scattering (SERS). This concept combines the spectroscopic advantages arising from maximum surface coverage and uniform molecular orientation of the Raman reporter molecules within the complete monolayer together with the high chemical and mechanical stability of the glass shell.

Synthesis, characterization, and biological studies of multidentate gold(i) and gold(iii) NHC complexes.

The synthesis and characterization of a novel macrocyclic Au(iii) N-heterocyclic carbene (NHC) imidazolyl complex, a novel macrocyclic tetra-NHC benzimidazole ligand, and the corresponding Ag(i) and Au(i) complexes are presented. Single-crystal X-ray diffraction analysis of the Au(i) benzimidazolyl complex 3 reveals an unusual structure, differing from the respective Au(i) imidazolyl complex 4. Both complexes have a Au4L2 composition; however, 3 has two C-Au(i)-C units acting as a connection between the two ligands with two Au(i) atoms being linearly coordinated inside the cavity of the macrocyclic ligand. In the case of complex 4, the structure shows a box-type coordination with all four Au(i) atoms being located between the two ligands. Stability studies in cell culture medium are performed for subsequent MTT assays and they show an unprecedented proton-to-deuterium exchange of the methylene bridge of the Au(iii) imidazolyl complex. In MTT assays, the tetranuclear acyclic Au(i) complex 5 displays the lowest IC50 values in MCF-7, PC3, and A2780cisR cells with a selective cytotoxicity for MCF-7 and A2780cisR cells.

Direct silica encapsulation of self-assembled-monolayer-based surface-enhanced Raman scattering labels with complete surface coverage of Raman reporters by noncovalently bound silane precursors.

Silica-coated surface-enhanced Raman scattering (SERS) labels with a self-assembled monolayer (SAM) on the entire surface of the metal colloid combine high chemical and mechanical stability with bright and reproducible Raman signals due to the complete surface coverage and uniform molecular orientation within the SAM. Currently available chemical syntheses are either based on the direct encapsulation of covalently bound silane precursors or comprise several steps, such as the sequential addition of noncovalently bound polyelectrolytes to render the surface vitreophilic. Here, a generic approach for the direct and fast silica encapsulation of commercially available Raman reporter molecules with polar head groups by noncovalently bound silane precursors is reported. The formation of highly SERS-active silica-coated clusters during silica encapsulation is determined by several parameters, in particular the type of Raman reporter molecule, the solvent, and the type and amount of the silane precursor.

Femtogram detection of cytokines in a direct dot-blot assay using SERS microspectroscopy and hydrophilically stabilized Au-Ag nanoshells.

Rapid parallel detection of two cytokines (IL-6 and IL-8) with femtogram sensitivity in a simple direct dot-blot assay is demonstrated. The microspectroscopic SERS acquisition scheme employs rationally designed, hydrophilically stabilized Au-Ag nanoshells as SERS labels, which are optimized for signal enhancement upon red laser excitation.

Single gold trimers and 3D superstructures exhibit a polarization-independent SERS response.

Dimers of metal nanospheres are well-known for their characteristic anisotropic optical response. Here, we demonstrate in single-particle SERS experiments that individual gold trimers and 3D superstructures exhibit a polarization-independent SERS response. This optical behavior of single particle clusters provides constant SERS signals, independent of the mutual orientation of the incident laser polarization and the plasmonic nanostructure, which is desired or even required in many SERS applications.