Self-assembly of spherical and rod-shaped nanoparticles with full positional control.

The controlled positioning of spherical gold nanoparticles and gold nanorods upon self-assembly on a substrate is of great interest for the fabrication of tailored plasmonic devices. Here, an electrostatic approach with a sequential two-step assembly protocol is presented as a cost-effective and high-yield alternative to previously presented, more complex proof of concepts. Three different geometries can be separately produced in large quantities relying on electrostatic attraction and repulsion of the charge-carrying building blocks: a single gold nanoparticle at the tip, the side or on top of a gold nanorod. DLVO theory is used to explain the electrostatic assembly strategy. The process is highly efficient and assembly yields between 79% (at the tip) and 94% (for the nanoparticle at the long side of the nanorod) are achieved.

Isomerism control of diethylstilbestrol by metal surface induced O-H cleavage.

Diethylstilbestrol (DES) is studied on Ag(111) and Cu(111) surfaces using X-ray photoelectron spectroscopy (XPS) and scanning tunnelling microscopy (STM). We find that DES molecules on the silver surface adsorb intact and adopt a trans-conformation. On the more reactive copper surface, O-H bond cleavage results in molecular adsorption in the cis-conformation, thus providing the means of obtaining different adsorption geometries. The difference in isomerism is reflected in the observed self-assemblies which exhibit room-temperature stability.

Plasmonic Nanolenses: Electrostatic Self-Assembly of Hierarchical Nanoparticle Trimers and Their Response to Optical and Electron Beam Stimuli.

Asymmetric nanoparticle trimers composed of particles with increasing diameter act as "plasmonic lenses" and have been predicted to exhibit ultrahigh confinement of electromagnetic energy in the space between the two smallest particles. Here we present an electrostatic self-assembly approach for creating gold nanoparticle trimers with an assembly yield of over 60%. We demonstrate that the trimer assembly leads to characteristic red-shifts and show the localization of the relevant plasmon modes by means of cathodoluminescence and electron energy loss spectroscopy. The results are analyzed in terms of surface plasmon hybridization.

Dynamics of Spatially Confined Bisphenol A Trimers in a Unimolecular Network on Ag(111).

Bisphenol A (BPA) aggregates on Ag(111) shows a polymorphism between two supramolecular motifs leading to formation of distinct networks depending on thermal energy. With rising temperature a dimeric pairing scheme reversibly converts into a trimeric motif, which forms a hexagonal superstructure with complex dynamic characteristics. The trimeric arrangements notably organize spontaneously into a self-assembled one-component array with supramolecular BPA rotors embedded in a two-dimensional stator sublattice. By varying the temperature, the speed of the rotors can be controlled as monitored by direct visualization. A combination of scanning tunneling microscopy and dispersion-corrected density-functional tight-binding (DFTB-vdW(surf)) based molecular modeling reveals the exact atomistic position of each molecule within the assembly as well as the driving force for the formation of the supramolecular rotors.

Surface-Assisted Cyclodehydrogenation; Break the Symmetry, Enhance the Selectivity.

Selectivity in chemical reactions is a major objective in industrial processes to minimize spurious byproducts and to save scarce resources. In homogeneous catalysis the most important factor which determines selectivity is structural symmetry. However, a transfer of the symmetry concept to heterogeneous catalysis still requires a detailed comprehension of the underlying processes. Here, we investigate a ring-closing reaction in surface-confined meso-substituted porphyrin molecules by scanning tunneling microscopy, temperature-programmed desorption, and computational modeling. The identification of reaction intermediates enables us to analyze the reaction pathway and to conclude that the symmetry of the porphyrin core is of pivotal importance regarding product yields.

Temperature-dependent templated growth of porphine thin films on the (111) facets of copper and silver.

The templated growth of the basic porphyrin unit, free-base porphine (2H-P), is characterized by means of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy measurements and density functional theory (DFT). The DFT simulations allow the deconvolution of the complex XPS and NEXAFS signatures into contributions originating from five inequivalent carbon atoms, which can be grouped into C-N and C-C bonded species. Polarization-dependent NEXAFS measurements reveal an intriguing organizational behavior: On both Cu(111) and Ag(111), for coverages up to one monolayer, the molecules adsorb undeformed and parallel to the respective metal surface. Upon increasing the coverage, however, the orientation of the molecules in the thin films depends on the growth conditions. Multilayers deposited at low temperatures exhibit a similar average tilting angle (30° relative to the surface plane) on both substrates. Conversely, for multilayers grown at room temperature a markedly different scenario exists. On Cu(111) the film thickness is self-limited to a coverage of approximately two layers, while on Ag(111) multilayers can be grown easily and, in contrast to the bulk 2H-P crystal, the molecules are oriented perpendicular to the surface. This difference in molecular orientation results in a modified line-shape of the C 1s XPS signatures, which depends on the incident photon energy and is explained by comparison with depth-resolved DFT calculations. Simulations of ionization energies for differently stacked molecules show no indication for a packing-induced modification of the multilayer XP spectra, thus indicating that the comparison of single molecule calculations to multilayer data is justified.

Self-assembly and chemical modifications of bisphenol a on Cu(111): interplay between ordering and thermally activated stepwise deprotonation.

Bisphenol A (BPA) is a chemical widely used in the synthesis pathway of polycarbonates for the production of many daily used products. Besides other adverse health effects, medical studies have shown that BPA can cause DNA hypomethylation and therefore alters the epigenetic code. In the present work, the reactivity and self-assembly of the molecule was investigated under ultra-high-vacuum conditions on a Cu(111) surface. We show that the surface-confined molecule goes through a series of thermally activated chemical transitions. Scanning tunneling microscopy investigations showed multiple distinct molecular arrangements dependent on the temperature treatment and the formation of polymer-like molecular strings for temperatures above 470 K. X-ray photoelectron spectroscopy measurements revealed the stepwise deprotonation of the hydroxy groups, which allows the molecules to interact strongly with the underlying substrate as well as their neighboring molecules and therefore drive the organization into distinct structural arrangements. On the basis of the combined experimental evidence in conjunction with density functional theory calculations, structural models for the self-assemblies after the thermal treatment were elaborated.