Synthesis and Investigation of a Soluble Distannene with no Trans-Bent Angle or Twisting in the Solid-State.

By treating KSiiPr3 with Sn[N(SiMe3)2]2 the distannene Sn2(TIPS)4 (TIPS=SiiPr3) is formed in a metathesis reaction. The crystal structure analysis of Sn2(TIPS)4 reveals a planar arrangement of the substituents in the solid-state and hence the second planar alkene like distannene of its kind. Due to the TIPS substituents, Sn2(TIPS)4 is well soluble in all commonly used organic solvents, opening the door for various analytics and reactivity studies. Due to its stability in solution, various reactions can be performed such as cycloaddition reactions with 2,3-dimethyl-1,3-butadiene (DMBD) and TMS-azide.

Au30(PiPr2nBu)12Cl6-An Open Cluster Provides Insight into the Influence of the Sterical Demand of the Phosphine Ligand in the Formation of Metalloid Gold Clusters.

Phosphine-stabilized gold clusters are an important subgroup of metalloid gold cluster compounds and are important model compounds for nanoparticles. Although there are numerous gold clusters with different phosphine ligands, the effect of phosphine on cluster formation and structure remains unclear. While the linear alkyl-substituted phosphine gold chlorides result in a Au32 cluster, the bulky tBu3P leads to a Au20 cluster. The reduction of (iPr2nBuP)AuCl, with the steric demand of the phosphine ligand between the mentioned phosphines, results in the successful synthesis and crystallization of a new metalloid gold cluster, Au30(PiPr2nBu)12Cl6. Its structure is similar to the Au32 cluster but with two missing AuCl units. The UV/Vis studies and quantum chemical calculations show the similarities between the two clusters and the influence of the phosphine ligand in the synthesis of metalloid gold clusters.

Multilayer Langmuir Film of Monodisperse Au Nanoclusters: Unusual Growth via Bilayers.

The assembly of nanomaterials into thin films is an important area in the nanofabrication of novel devices. The monodispersity of nanoparticles plays an essential role in the resulting quality of the assembled mono- and multilayers. Larger polydispersity leads to smaller lateral correlation lengths and smaller domains of aligned nanoparticles, thus resulting in more point and line defects. Perfectly monodisperse nanoparticles should therefore minimize the number of defects in the assembled films. Despite tremendous progress in reducing the polydispersity of nanoparticles, there has been limited research on the assembly of thin films out of perfectly monodisperse nanoclusters. Here, we show a formation of Langmuir films using perfectly monodisperse gold nanoclusters with composition Au32(nBu3P)12Cl8 exhibiting a diameter of 1.8 nm. Using both in situ and ex situ small-angle X-ray scattering, we show that the monolayer formed on a Langmuir-Blodgett trough exhibits long-range order. Moreover, after compressing the monolayer, we found that the stress accumulated prior to the monolayer collapse triggers a transition to a short-range order not previously reported. If such monolayer is compressed further, the second layer is not formed as in the case of standard nanoparticles. Instead, a growth of islands by an odd number of layers is observed, leading to a thin film with a structure consisting of two different orientations of the hexagonal lattice. Such anomalous behavior may have implications for the possibilities of thin-film formation.

Au20 (t Bu3 P)8 : A Highly Symmetric Metalloid Gold Cluster in Oxidation State 0.

Metalloid gold clusters have unique properties with respect to size and structure and are key intermediates in studying transitions between molecular compounds and the bulk phase of the respective metal. In the following, the synthesis of the all-phosphine protected metalloid cluster Au20 (t Bu3 P)8 , solely built from gold atoms in the oxidation state of 0 is reported. Single-crystal X-ray analysis revealed a highly symmetric hollow cube-octahedral arrangement of the gold atoms, resembling gold bulk structure. Quantum-chemical calculations illustrated the cluster can be described as a 20-electron superatom. Optical properties of the compound have shown molecular-like behavior.

Direct laser induced writing of high precision gold nanosphere SERS patterns.

The high sensitivity and molecular fingerprint capability of Surface-Enhanced Raman Spectroscopy (SERS) have lead to a wide variety of applications ranging from classical physics, chemistry over biology to medicine. Equally, there are numerous methods to fabricate samples owing to the desired properties and to create the localized surface plasmon resonances (LSPRS). However, for many applications the LSPRs must be specifically localized on micrometer sized areas and multiple steps of lithography are needed to achieve the desired substrates. Here we present a fast and reliable direct laser induced writing (DIW) method to produce SERS substrates with active areas of interest in any desired size and shape in the micrometer regime. Afterwards, the SERS substrates have been functionalized with phthalocyanines. The DIW fabricated samples realize sub-monolayer sensitivity and an almost uniform enhancement over the entire area, which make this production method suitable for many sensing applications.

Synthesis and characterisation of four bimetallic gold-gallium clusters with Au-Ga rings as a new structural motif in gold cluster chemistry.

Using the newly introduced reducing agent in gold cluster chemistry GaCp, four new bimetallic gold-gallium cluster compounds were synthesised, stabilised by alkylphosphine ligands. The gold core of Au6(GaCl2)4(PEt3)6, Au7(GaCl2)3(P n Pr3)6 and Au13(GaCl2)5(GaCl)(P n Pr2 n Bu)9 is composed of two, three and four Au4 tetrahedra, linked in different ways. This arrangement gives the last-mentioned cluster the shape of a five-pointed star. A fourth synthesised metalloid gold cluster Au13(GaCl2)5(P n Pr3)9 consists of a voluminous gold core encircled by a gold-gallium chain. These gold-gallium chains are present in all four cluster compounds and are similar to the well-known gold-sulphur staple motifs in thiol-stabilised gold cluster compounds.