Highly Ordered N-Heterocyclic Carbene Monolayers on Cu(111).

The benzannulated N-heterocyclic carbene, 1,3-dibenzylbenzimidazolylidene (NHC) forms large, highly ordered domains when adsorbed on Cu(111) under ultrahigh vacuum conditions. A combination of scanning tunnelling microscopy (STM), high-resolution electron energy loss spectroscopy (HREELS), and density functional theory (DFT) calculations reveals that the overlayer consists of vertical benzannulated NHC moieties coordinating to Cu adatoms. Long-range order results from the placement of the two benzyl substituents on opposite sides of the benzimidazole moiety, with their aromatic rings approximately parallel to the surface.

Strong Substrate Mediation of Attractive Lateral Interactions of CO on Cu(110).

The mechanism of chemical reactions between adsorbed species is defined by the combined effects of the adsorbate-substrate potential landscape and lateral interactions. Such lateral interactions are therefore integral to catalytic processes, but their study is often complicated by "substrate mediation", the regulation of a two-body potential between adsorbed particles by the surface itself. Substrate mediation can influence the sign and magnitude of lateral interactions.

5- Endo Cyclizations of NHC-Boraallyl Radicals Bearing Ester Substituents: Characterization of Derived 1,2-Oxaborole Radicals and Boralactones.

EPR studies of radical hydrogen abstraction reactions of N-heterocyclic carbene (NHC) complexes of alkenylboranes bearing two ester substituents revealed not the expected boraallyl radicals but instead isomeric 1,2-oaxborole radicals. Such radicals are new, and DFT calculations show that they arise from the initially formed boraallyl radicals by a rapid, exothermic 5- endo cyclization. These spectroscopic and computational discoveries prompted a series of preparative experiments that provided access to a novel family of robust NHC-boralactones.

On-Demand Final State Control of a Surface-Bound Bistable Single Molecule Switch.

Modern electronic devices perform their defined action because of the complete reliability of their individual active components (transistors, switches, diodes, and so forth). For instance, to encode basic computer units (bits) an electrical switch can be used. The reliability of the switch ensures that the desired outcome (the component's final state, 0 or 1) can be selected with certainty.

Homochiral Emissive Λ - and Δ -[Ir Pd ] Supramolecular Cages.

Synthetic self-assembly is a powerful technique for the bottom-up construction of discrete and well-defined polyhedral nanostructures resembling the spherical shape of large biological systems. In recent years, numerous Archimedean-shaped coordination cages have been reported based on the assembly of bent monodentate organic ligands containing two or more distal pyridyl rings and square-planar Pd ions. The formation of photoactive Pd metallamacrocycles and cages, however, remain rare.

Formation of bioinorganic complexes by the corrosive adsorption of (S)-proline on Ni/Au(111).

Nickel nanoparticles modified by the adsorption of chiral amino acids are known to be effective enantioselective heterogeneous catalysts. The leaching of nickel by amino acids has a number of potential effects including the induction of chirality in the nickel atoms left behind in the nanoparticle and the creation of catalytically active nickel complexes. The adsorption of (S)-proline onto Au(111) precovered by two-dimensional nickel nanoclusters was investigated by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and high-resolution electron energy loss spectroscopy.

Adsorption of a dihydro-TTF derivative on Au(111) via a thiolate complex bonding to gold adatoms.

A dihydro-TTF derivative with four acetyl-protected thiol ligands was synthesised and adsorbed on Au(111) under UHV conditions. Scanning Tunnelling Microscopy (STM) and Infrared (IR) spectroscopy show that self-organised structures are formed following annealing to 333 K, with each pair of bidentate thiolate ligands bonding to a single gold adatom in a S-Auad-S complex. Due to the lack of a direct orbital overlap between the dihydro-TTF moieties and the surface, relatively little charge transfer between TAT-TTF and the gold surface occurs.

The structure of (SCN)(x): a study using molecular and solid-state density functional theory calculations.

A riddle solved! Despite its simple formula, the structure of the (SCN)(x) polymer has remained elusive since its first synthesis in 1929. From energetics as well as NMR chemical shifts, based on DFT calculations, we have strong evidence that it is indeed a tangle of linear chains, made up from N-linked S(2)C(2)N five-membered rings.Molecular fragments and crystal structures based on proposed structures for polythiocyanogen were studied by using molecular and solid-state electronic structure calculations at the density functional theory level.