The directed assembly of gold nanoparticles is essential for their use in many kinds of applications, such as electronic devices, biological labels, and sensors. Herein an atomic alteration in the molecular structure of ligand-stabilized gold nanoparticles that can shift the interparticle distance up to 1 nm upon covalent coupling to organic-inorganic superstructures is presented. Gold nanoparticles are stabilized by two octadentate thioether ligands and have a mean diameter of 1.1 nm. The ligands contain a central rigid rod varying in length and terminally functionalized with a protected acetylene. The two peripheral functional groups on each particle enable the directed assembly of nanoparticles to dimers, trimers, and tetramers by oxidative acetylene coupling. This is a wet chemical protocol resulting in covalently bound nanoparticles. These organic-inorganic hybrid superstructures are analyzed by transmission electron microscopy, small angle X-ray scattering, and UV/vis spectroscopy. The focus of the comparison here is the subunit, which is anchoring the bridgehead, either a pyridine or benzene moiety. The pyridine-based ligands reflect the calculated length of the rigid-rod spacer in their interparticle distances in the obtained hybrid structures. This suggests a perpendicular arrangement that results from the coordination of the pyridine's lone pair to the gold surface. An atomic variation in the ligand's center leads to smaller interparticle distances in the case of hybrid structures obtained from benzene ligands. This large difference in the spatial arrangement suggests a tangential arrangement of the interparticle bridging structure in the latter case. Consequently a rather flat arrangement parallel to the particle surface must be assumed for the central benzene unit of the benzene-based ligand.

Ligand-stabilized gold nanoparticles (Au NPs) are promising materials for nanotechnology with applications in electronics, catalysis, and sensors. These applications depend on the ability to synthesize stable and monodisperse NPs. Herein, the design and synthesis of two series of dendritic thioether ligands and their ability to stabilize Au NPs is presented. The dendrimers have 1,3,5-trisubstituted benzene branching units bridged by either meta-xylene or ethylene moieties. A comparison between the two ligands shows how both size control and the stability of the NPs are influenced by the nature of the ligand-NP wrapping interaction. The meta-xylene-bridged ligands provided NPs with a narrow size distribution centered around a diameter of 1.2 nm, whereas the NPs formed with ethylene-bridged dendrimers lack long-term stability with NP aggregation detected by UV/Vis spectroscopy and transmission electron microscopy. The bulkier tert-butyl-functionalized meta-xylene bridges form larger ligand shells that inhibit further growth of the NPs and thus provide a simple route to stable and monodisperse Au NPs that may find use as functional components in nanoelectronic devices.

The assembly of dumbbell structures as organic-inorganic hybrid materials is presented. Gold nanoparticles (NPs) with a mean diameter of 1.3 nm were synthesized in very good yields using a stabilizing dendrimer based on benzylic thioether subunits. The extended dendritic ligand covers the NP surface and contains a peripheral protected acetylene, providing coated and monofunctionalized NPs. These NPs themselves can be considered as large molecules, and thus, applying a wet-chemical deprotection/oxidative acetylene coupling protocol exclusively provides dimers of NPs interlinked by a diethynyl bridge. The concept not only enables access to novel organic/inorganic hybrid architectures but also promises new approaches in labeling technology.

The formation of true single-molecule complexes between organic ligands and nanoparticles is challenging and requires careful design of molecules with size, shape, and chemical properties tailored for the specific nanoparticle. Here we use computer simulations to describe the atomic-scale structure, dynamics, and energetics of ligand-mediated synthesis and interlinking of 1 nm gold clusters. The models help explain recent experimental results and provide insight into how multidentate thioether dendrimers can be employed for synthesis of true single-ligand-nanoparticle complexes and also nanoparticle-molecule-nanoparticle "dumbbell" nanostructures. Electronic structure calculations reveal the individually weak thioether-gold bonds (325 ± 36 meV), which act collectively through the multivalent (multisite) anchoring to stabilize the ligand-nanoparticle complex (∼7 eV total binding energy) and offset the conformational and solvation penalties involved in this "wrapping" process. Molecular dynamics simulations show that the dendrimer is sufficiently flexible to tolerate the strained conformations and desolvation penalties involved in fully wrapping the particle, quantifying the subtle balance between covalent anchoring and noncovalent wrapping in the assembly of ligand-nanoparticle complexes. The computed preference for binding of a single dendrimer to the cluster reveals the prohibitively high dendrimer desolvation barrier (1.5 ± 0.5 eV) to form the alternative double-dendrimer structure. Finally, the models show formation of an additional electron transfer channel between nitrogen and gold for ligands with a central pyridine unit, which gives a stiff binding orientation and explains the recently measured larger interparticle distances for particles synthesized and interlinked using linear ligands with a central pyridine rather than a benzene moiety. The findings stress the importance of organic-inorganic interactions, the control of which is central to the rational engineering and eventual large-scale production of functional building blocks for nano(bio)electronics.

The controlled assembly of gold nanoparticles in terms of the spatial arrangement and number of particles is essential for many future applications like electronic devices, sensors and labeling. Here an approach is presented to build up oligomers of mono functionalized gold nanoparticles by the use of 1,3-bipolar azide alkyne cycloaddition click chemistry. The gold nanoparticles of 1.3 nm diameter are stabilized by one dendritic thioether ligand comprising an alkyne function. Together with di-, tri- and tetra-azide linker molecules the gold nanoparticle can be covalently coupled by a wet chemical protocol. The reaction is tracked with IR and UV-vis spectroscopy and the yielded organic-inorganic hybrid structures are analyzed by transmission electron microscopy. To evaluate the success of this click chemistry reaction statistical analysis of the formed oligomers is performed. The geometric and spatial arrangements of the found oligomers match perfectly the calculated values for the used linker molecules. Dimers, trimers and tetramers could be identified after the reaction with the corresponding linker molecule. The results of this model reaction suggest that the used click chemistry protocol is working well with mono functionalized gold nanoparticles.