Interaction of chiral L-dialanine with Cu(100).

We report on the properties of the thin films of the short peptide L-dialanine grown on Cu(100) surfaces and compare them to those of L-alanine by using surface techniques like XPS, IRRAS and STM. The first dialanine monolayer, in contact with the metallic substrate, is found to consist of whole neutral molecules in the non-zwitterionic state forming a c(2 × 4) pattern with quasi-hexagonal symmetry. The peptide bond of dialanine is preserved in the adsorption state. The ordering of the L-dialanine overlayer is shown to replicate rearrangements of the atoms of the substrate around dislocations of the latter indicating a strong molecule-surface interaction. In the multilayer regime, molecules of the second and further layers are found to be in a zwitterionic state, readily desorbing even at room temperature. The first dialanine layer is tightly bound to the substrate, begins to desorb at temperatures higher than 390 K and cracks down at the surface, transforming into a new moiety, beyond 435 K.

Surface-Guided Formation of an Organocobalt Complex.

Organocobalt complexes represent a versatile tool in organic synthesis as they are important intermediates in Pauson-Khand, Friedel-Crafts, and Nicholas reactions. Herein, a single-molecule-level investigation addressing the formation of an organocobalt complex at a solid-vacuum interface is reported. Deposition of 4,4'-(ethyne-1,2-diyl)dibenzonitrile and Co atoms on the Ag(111) surface followed by annealing resulted in genuine complexes in which single Co atoms laterally coordinated to two carbonitrile groups undergo organometallic bonding with the internal alkyne moiety of adjacent molecules. Alternative complexation scenarios involving fragmentation of the precursor were ruled out by complementary X-ray photoelectron spectroscopy. According to density functional theory analysis, the complexation with the alkyne moiety follows the Dewar-Chatt-Duncanson model for a two-electron-donor ligand where an alkyne-to-Co donation occurs together with a strong metal-to-alkyne back-donation.

Phase control and lateral heterostructures of MoTe2 epitaxially grown on graphene/Ir(111).

Engineering the growth of the different phases of two-dimensional transition metal dichalcogenides (2D-TMDs) is a promising way to exploit their potential since the phase determines their physical and chemical properties. Here, we report on the epitaxial growth of monolayer MoTe2 on graphene on an Ir(111) substrate. Scanning tunneling microscopy and spectroscopy provide insights into the structural and electronic properties of the different polymorphic phases, which remain decoupled from the substrate due to the weak interaction with graphene. In addition, we demonstrate a great control of the relative coverage of the relevant 1T' and 1H MoTe2 phases by varying the substrate temperature during the growth. In particular, we obtain large areas of the 1T' phase exclusively or the coexistence of both phases with different ratios.

Switchable molecular functionalization of an STM tip: from a Yu-Shiba-Rusinov Tip to a Kondo tip.

In this work we fabricate and characterize a functionalized superconducting (SC) Nb tip of a scanning tunnelling microscope (STM). The tip is functionalized with a Tetracyanoquinodimethane molecule (TCNQ) that accepts charge from the tip and develops a magnetic moment. As a consequence, in scanning tunnelling spectroscopy (STS), sharp, bias symmetric sub-gap states identified as Yu-Shiba-Rusinov (YSR) bound states appear against the featureless density of states of a metallic graphene on Ir(111) sample. Although the coupling regime of the magnetic impurity with the SC tip depends on the initial absorption configuration of the molecule, the interaction strength between the SC tip and the charged TCNQ molecule can be reversibly controlled by tuning the tip-sample distance. The controlled transition from one coupling regime to the other allows us to verify the relation between the energy scales of the two competing many-body effects for the functionalized tip. Quenching the SC state of the Nb tip with a magnetic field switches abruptly from a tip dominated by the YSR bound states to a Kondo tip.