Interplay between Switching Driven by the Tunneling Current and Atomic Force of a Bistable Four-Atom Si Quantum Dot.

We assemble bistable silicon quantum dots consisting of four buckled atoms (Si4-QD) using atom manipulation. We demonstrate two competing atom switching mechanisms, downward switching induced by tunneling current of scanning tunneling microscopy (STM) and opposite upward switching induced by atomic force of atomic force microscopy (AFM). Simultaneous application of competing current and force allows us to tune switching direction continuously. Assembly of the few-atom Si-QDs and controlling their states using versatile combined AFM/STM will contribute to further miniaturization of nanodevices.

Sublattice localized electronic states in atomically resolved graphene-Pt(111) edge-boundaries.

Understanding the connection of graphene with metal surfaces is a necessary step for developing atomically precise graphene-based technology. Combining high-resolution STM experiments and DFT calculations, we have unambiguously unveiled the atomic structure of the boundary between a graphene zigzag edge and a Pt(111) step. The graphene edges minimize their strain by inducing a 3-fold edge-reconstruction on the metal side. We show the existence of an unoccupied electronic state that is mostly localized on the C-edge atoms of one particular graphene sublattice, which could have implications in the design of graphene based devices.

Understanding scanning tunneling microscopy contrast mechanisms on metal oxides: a case study.

A comprehensive analysis of contrast formation mechanisms in scanning tunneling microscopy (STM) experiments on a metal oxide surface is presented with the oxygen-induced (2√2×√2)R45° missing row reconstruction of the Cu(100) surface as a model system. Density functional theory and electronic transport calculations were combined to simulate the STM imaging behavior of pure and oxygen-contaminated metal tips with structurally and chemically different apexes while systematically varying bias voltage and tip-sample distance. The resulting multiparameter database of computed images was used to conduct an extensive comparison with experimental data. Excellent agreement was attained for a large number of cases, suggesting that the assumed model tips reproduce most of the commonly encountered contrast-determining effects. Specifically, we find that depending on the bias voltage polarity, copper-terminated tips allow selective imaging of two structurally distinct surface Cu sites, while oxygen-terminated tips show complex contrasts with pronounced asymmetry and tip-sample distance dependence. Considering the structural and chemical stability of the tips reveals that the copper-terminated apexes tend to react with surface oxygen at small tip-sample distances. In contrast, oxygen-terminated tips are considerably more stable, allowing exclusive surface oxygen imaging at small tip-sample distances. Our results provide a conclusive understanding of fundamental STM imaging mechanisms, thereby providing guidelines for experimentalists to achieve chemically selective imaging by properly selecting imaging parameters.

Zirconocene-mediated synthesis of cyclobutabenzenes.

A new, mild, one-pot method for the synthesis of cyclobutabenzenes by the zirconium-promoted cross-coupling reaction of aryllithium compounds and alkenyl bromides is reported. Formation of an arynezirconocene complex and its regioselective coupling with an alkenyl bromide are the key steps of the process. This method allows the regio- and diastereoselective synthesis of functionalized cyclobutabenzene derivatives from simple and easily available starting materials.

Medium-sized carbocycles by a zirconocene-catalyzed tandem formal ring expansion-magnesation reaction of alkenyl-substituted cyclic enol ethers.

A new regio- and stereoselective zirconocene-catalyzed reaction for the synthesis of medium-sized rings is described. The global reaction supposes a formal ring expansion of a cyclic enol ether to give a functionalized carbocycle.

Coupling reactions of zirconocene complexes and heterosubstituted alkenes.

This tutorial review surveys recent advances in the field of zirconium promoted coupling reactions of unsaturated molecules (and/or organolithium compounds) and heterosubstituted alkenes. This reaction has recently emerged as a powerful tool in organic chemistry to access a variety of synthetically useful building blocks not easily available by other methods. In particular, three different reaction pathways are discussed: i) the reaction involving alkyne-zirconocene and aryne-zirconocene complexes which allows access to dienyl and aryl zirconocene complexes; ii) the reaction of alkene-zirconocene complexes and enol ethers which has shown to be highly dependent on the structure of the enol ether used, allowing the synthesis of simple vinyl zirconocenes or multicomponent coupling products, and; iii) the reaction involving imine-zirconocene complexes which supposes a new entry to allylic amines.

Zirconium-mediated cross-coupling of terminal alkynes and vinyl bromides: selective synthesis of cyclobutene and 1,3-diene derivatives.

A diastereoselective synthesis of 1,3-butadiene or cyclobutene derivatives by a zirconium-mediated reaction of alkenyllithium compounds and vinyl bromides is reported. The key steps involve the generation of zirconocene-alkyne complexes from haloalkenes and subsequent coupling with alkenyl bromides. Thus, formally the process supposes the cross-coupling reaction between a terminal alkyne and an alkenyl bromide. Moreover, the use of butyl vinyl ether instead of vinyl bromide as the unsaturated system allows an alternative access to different 1,3-butadiene regioisomers.

Zirconium-mediated coupling reactions of amines and enol or allyl ethers: synthesis of allyl- and homoallylamines.

An easy and efficient zirconium-mediated synthesis of allylamines from simple amines and enol ethers is described. This strategy also allows the synthesis of amino alcohol derivatives containing a Z double bond in their structure when 2,3-dihydrofuran is used. Simple conventional modification of these amino alcohols leads to 2-substituted piperidine derivatives. By applying this approach, a formal total synthesis of the alkaloid coniine is easily achieved from a protected butylamine. Finally, the zirconium-mediated reaction of amines and allyl phenyl ether furnishes homoallylamines or amino ethers depending on the structure of the starting amine.