Fully Reprogrammable 2D Array of Multistate Molecular Switching Units.

Integration of molecular switching units into complex electronic circuits is considered to be the next step toward the realization of novel logic and memory devices. This paper reports on an ordered 2D network of neighboring ternary switching units represented by triazatruxene (TAT) molecules organized in a honeycomb lattice on a Ag(111) surface. Using low-temperature scanning tunneling microscopy, the bonding configurations of individual TAT molecules can be controlled, realizing up to 12 distinct states per molecule. The switching between those states shows a strong bias dependence ranging from tens of millivolts to volts. The low-bias switching behavior is explored in active units consisting of two and more interacting TAT molecules that are purposefully defined (programmed) by high-bias switching within the honeycomb lattice. Within such a unit the low-bias switching can be triggered and accessed by single-point measurements on a single TAT molecule, demonstrating up to 9 and 19 distinguishable states in a dyad and a tetrad of coupled molecules, respectively. High experimental control over the desired state, owing to bias-dependent hierarchical switching and pronounced switching directionality, as well as full reversibility, make this system particularly appealing, paving the way to design complex molecule-based memory systems.

The odd-number cyclo[13]carbon and its dimer, cyclo[26]carbon.

Molecular rings of N carbon atoms (cyclo[N]carbons, or CN) are excellent benchmarking systems for testing quantum chemical theoretical methods and valuable precursors to other carbon-rich materials. Odd-N cyclocarbons, which have been elusive to date, are predicted to be even less stable than even-N cyclocarbons. We report the on-surface synthesis of cyclo[13]carbon, C13, by manipulation of decachlorofluorene with a scanning probe microscope tip. We elucidated the properties of C13 by experiment and theoretical modeling. C13 adopts an open-shell configuration with a triplet ground state and a kinked geometry, which shows different extents of distortion and carbene localization depending on the molecular environment. Moreover, we prepared and characterized the C13 dimer, cyclo[26]carbon, demonstrating the potential of cyclocarbons and their precursors as building blocks for carbon allotropes.

Ferrocenyl-Substituted Triazatruxenes: Synthesis, Electronic Properties, and the Impact of Ferrocenyl Residues on Directional On-Surface Switching on Ag(111).

We report on seven new ferrocenyl-(1, 3)- and ferrocenylethynyl-modified N,N',N″-triethyltriazatruxenes (EtTATs) 4-7 as well as the dodecyl counterpart 2 of compound 1 and their use as molecular switching units when deposited on a Ag(111) surface. Such functional units may constitute a new approach to molecule-based high-density information storage and processing. Besides the five compounds 1-3, 6, and 7, where the 3-fold rotational symmetry of the triazatruxene (TAT) template is preserved, we also included 2-ethynylferrocenyl-TAT 4 and 2,2'-di(ethynylferrocenyl)-TAT 5, whose mono- and disubstitution patterns break the 3-fold symmetry of the TAT core. Voltammetric studies indicate that the ferrocenyl residues of compounds 1-7 oxidize prior to the oxidation of the TAT core. We have noted strong electrostatic effects on TAT oxidation in the 2,2',2″-triferrocenyl-TAT derivatives 1 and 2 and the 3,3',3″-isomer 3. The oxidized complexes feature multiple electronic excitations in the near-infrared and the visible spectra, which are assigned to dδ/δ* transitions of the ferrocenium (Fc+) moieties, as well as TAT → Fc+ charge-transfer transitions. The latter are augmented by intervalence charge-transfer contributions Fc → Fc+ in mixed-valent states, where only a part of the available ferrocenyl residues is oxidized. EtTAT was previously identified as a directional three-level switching unit when deposited on Ag(111) and constitutes a trinary-digit unit for on-surface information storage. The symmetrically trisubstituted compound 6 retains this property, albeit at somewhat reduced switching rates due to the additional interaction between the ferrocenyl residues and the Ag surface. In particular, the high directionality at low bias and the inversion of the preferred sense of the on-surface rocking motion with either a clockwise or counterclockwise switching sense, depending on the identity of the surface enantiomer, are preserved. Unsymmetrical substitution in mono- and diferrocenylated 4 and 5 alters the underlying ratchet potential in a manner such that a two-state switching between the two degenerate surface conformations of 4 or a pronounced suppression of switching (5) is observed.

Imaging the Single-Electron Ln-Ln Bonding Orbital in a Dimetallofullerene Molecular Magnet.

Chemically robust single-molecule magnets (SMMs) with sufficiently high blocking temperatures TB are among the key building blocks for the realization of molecular spintronic or quantum computing devices. Such device applications require access to the magnetic system of a SMM molecule by means of electronic transport, which primarily depends on the interaction of magnetic orbitals with the electronic states of the metallic electrodes. Scanning tunneling microscopy in combination with ab initio calculations allows to directly address the unoccupied component of the single-electron molecular orbital that mediates the ferromagnetic exchange coupling between two 4f ions within a lanthanide endohedral dimetallofullerene deposited on a graphene surface. The single-electron metal-metal bond provides a direct access to the molecule's magnetic system in the transport experiments, paving the way for investigation and controlled manipulation of the spin system of individual dimetallofullerene SMMs, essential for molecular spintronics.

Exceptionally High Blocking Temperature of 17 K in a Surface-Supported Molecular Magnet.

Single-molecule magnets (SMMs) are among the most promising building blocks for future magnetic data storage or quantum computing applications, owing to magnetic bistability and long magnetic relaxation times. The practical device integration requires realization of 2D surface assemblies of SMMs, where each magnetic unit shows magnetic relaxation being sufficiently slow at application-relevant temperatures. Using X-ray absorption spectroscopy and X-ray magnetic circular dichroism, it is shown that sub-monolayers of Dy2 @C80 (CH2 Ph) dimetallofullerenes prepared on graphene by electrospray deposition exhibit magnetic behavior fully comparable to that of the bulk. Magnetic hysteresis and relaxation time measurements show that the magnetic moment remains stable for 100 s at 17 K, marking the blocking temperature TB(100) , being not only in excellent agreement with that of the bulk sample but also representing by far the highest one detected for a surface-supported single-molecule magnet. The reported findings give a boost to the efforts to stabilize and address the spin degree of freedom in molecular magnets aiming at the realization of SMM-based spintronic units.

Tip-Induced Inversion of the Chirality of a Molecule's Adsorption Potential Probed by the Switching Directionality.

The switching behavior of surface-supported molecular units excited by current, light, or mechanical forces is determined by the shape of the adsorption potential. The ability to tailor the energy landscape in which a molecule resides at a surface gives the possibility of imposing a desired response, which is of paramount importance for the realization of molecular electronic units. Here, by means of scanning tunneling microscopy, a triazatruxene (TAT) molecule on Ag(111) is studied, which shows a switching behavior characterized by transitions of the molecule between three states, and which is attributed to three energetically degenerate bonding configurations. Upon tunneling current injection, the system can be excited and continuously driven, showing a switching directionality close to 100%. Two surface enantiomers of TAT show opposite switching directions pointing at the chirality of the energy landscape of the adsorption potential as a key ingredient for directional switching. Further, it is shown that by tuning the tunneling parameters, the symmetry of the adsorption potential can be controllably adjusted, leading to a suppression of the directionality or an inversion of the switching direction. The findings represent a molecule-surface model system exhibiting unprecedented control of the shape of its adsorption potential.

Bulk-Like Magnetic Signature of Individual Fe4H Molecular Magnets on Graphene.

Single-molecule magnets (SMMs) incorporate key properties that make them promising candidates for the emerging field of spintronics. The challenge to realize ordered SMM arrangements on surfaces and at the same time to preserve the magnetic properties upon interaction with the environment is a crucial point on the way to applications. Here we employ inelastic electron tunneling spectroscopy (IETS) to address the magnetic properties in single Fe4 complexes that are adsorbed in a highly ordered arrangement on graphene/Ir(111). We are able to substantially reduce the influence of both the tunneling tip and the adsorption environment on the Fe4 complex during the measurements by using appropriate tunneling parameters in combination with the flat-lying Fe4H derivative and a weakly interacting surface. This allows us to perform noninvasive IETS studies on these bulky molecules. From the measurements we identify intermultiplet spin transitions and determine the intramolecular magnetic exchange interaction constant on a large number of molecules. Although a considerable scattering of the exchange constant values is observed, the distribution maximum is located at a value that coincides with that of the bulk. Our findings confirm a retained molecular magnetism of the Fe4H complex at the local scale and evaluate the influence of the environment on the magnetic exchange interaction.

The graphene/n-Ge(110) interface: structure, doping, and electronic properties.

The implementation of graphene in semiconducting technology requires precise knowledge about the graphene-semiconductor interface. In our work the structure and electronic properties of the graphene/n-Ge(110) interface are investigated on the local (nm) and macro (from µm to mm) scales via a combination of different microscopic and spectroscopic surface science techniques accompanied by density functional theory calculations. The electronic structure of freestanding graphene remains almost completely intact in this system, with only a moderate n-doping indicating weak interaction between graphene and the Ge substrate. With regard to the optimisation of graphene growth it is found that the substrate temperature is a crucial factor, which determines the graphene layer alignment on the Ge(110) substrate during its growth from the atomic carbon source. Moreover, our results demonstrate that the preparation route for graphene on the doped semiconducting material (n-Ge) leads to the effective segregation of dopants at the interface between graphene and Ge(110). Furthermore, it is shown that these dopant atoms might form regular structures at the graphene/Ge interface and induce the doping of graphene. Our findings help to understand the interface properties of the graphene-semiconductor interfaces and the effect of dopants on the electronic structure of graphene in such systems.

Uniaxial 2D Superlattice of Fe4 Molecular Magnets on Graphene.

We demonstrate that electrospray deposition enables the fabrication of highly periodic self-assembled arrays of Fe4H single molecule magnets on graphene/Ir(111). The energetic positions of molecular states are probed by means of scanning tunneling spectroscopy, showing pronounced long- and short-ranged spatial modulations, indicating the presence of both locally varying intermolecular as well as adsorption-site dependent molecule-substrate interactions. From the magnetic field dependence of the X-ray magnetic circular dichroism signal, we infer that the magnetic easy axis of each Fe4H molecule is oriented perpendicular to the sample surface and that after the deposition the value of the uniaxial anisotropy is identical to the one in bulk. Our findings therefore suggest that the observed interaction of the molecules with their surrounding does not modify the molecular magnetism, resulting in a two-dimensional array of molecular magnets that retain their bulk magnetic properties.