Variable-temperature lightwave-driven scanning tunneling microscope with a compact, turn-key terahertz source.

We report on a lightwave-driven scanning tunneling microscope based on a home-built microscope and a compact, commercial, and cost-effective terahertz-generation unit with a repetition rate of 100 MHz. The measurements are performed in an ultrahigh vacuum at temperatures between 8.5 and 300 K. The cross-correlation of the pump and probe pulses indicates a temporal resolution on the order of a picosecond. In terms of spatial resolution, CO molecules, step edges, and atomically resolved terraces are readily observed in terahertz images, with sometimes better contrast than in the topographic and (DC) current channels. The utilization of a compact, turn-key terahertz-generation system requires only limited experience with optics and terahertz generation, which may facilitate the deployment of the technique to further research groups.

Molybdenum(0)-Tricarbonyl Complex Supported by an Azacalix-pyridine Ligand: Synthesis, Characterization, Surface Deposition and Conversion to a Molybdenum(VI)-Trioxo Complex with O2.

Adsorption of metal-organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining the advantages of homogeneous and heterogeneous catalysis. To avoid the "surface trans-effect" a dome-shaped molybdenum(0) tricarbonyl complex supported by an tolylazacalix[3](2,6)pyridine ligand is synthesized. This vacuum-evaporable complex both activates CO and reacts with molecular oxygen (O2) to form a Mo(VI) trioxo complex which in turn is capable of catalytically mediating oxygen transfer. The molybdenum tricarbonyl- and trioxo complexes are investigated in the solid state, in homogeneous solution and on noble metal surfaces (Cu, Au) employing a range of spectroscopic and analytical methods.

Spin-Crossover and Fragmentation of Fe(neoim)2 on Silver and Gold.

The neutral spin crossover complex Fe(neoim)2, neoim being the deprotonated form of the ionogenic ligand 2-(1H-imidazol-2-yl)-9-methyl-1,10-phenanthroline (neoimH), is investigated on the (111) surfaces of Au and Ag using scanning tunneling microscopy and density functional theory calculations. The complex sublimates and adsorbs intact on Ag(111), where it exhibits an electron-induced spin crossover. However, it fragments on Au. According to density functional theory calculations, the adsorbed complex is drastically distorted by the interactions with the substrates, in particular by van der Waals forces. Dispersion interaction is also decisive for the relative stabilities of the low- and high-spin states of the adsorbed complex. The unexpected instability of the complex on the gold substrate is attributed to enhanced covalent bonding of the fragments to the substrate.

Defying the inverse energy gap law: a vacuum-evaporable Fe(ii) low-spin complex with a long-lived LIESST state.

The novel vacuum-evaporable complex [Fe(pypypyr)2] (pypypyr = bipyridyl pyrrolide) was synthesised and analysed as bulk material and as a thin film. In both cases, the compound is in its low-spin state up to temperatures of at least 510 K. Thus, it is conventionally considered a pure low-spin compound. According to the inverse energy gap law, the half time of the light-induced excited high-spin state of such compounds at temperatures approaching 0 K is expected to be in the regime of micro- or nanoseconds. In contrast to these expectations, the light-induced high-spin state of the title compound has a half time of several hours. We attribute this behaviour to a large structural difference between the two spin states along with four distinct distortion coordinates associated with the spin transition. This leads to a breakdown of single-mode behaviour and thus drastically decreases the relaxation rate of the metastable high-spin state. These unprecedented properties open up new strategies for the development of compounds showing light-induced excited spin state trapping (LIESST) at high temperatures, potentially around room temperature, which is relevant for applications in molecular spintronics, sensors, displays and the like.

Large Orbital Moment of Two Coupled Spin-Half Co Ions in a Complex on Gold.

The magnetic properties of transition-metal ions are generally described by the atomic spins of the ions and their exchange coupling. The orbital moment, usually largely quenched due the ligand field, is then seen as a perturbation. In such a scheme, S = 1/2 ions are predicted to be isotropic. We investigate a Co(II) complex with two antiferromagnetically coupled 1/2 spins on Au(111) using low-temperature scanning tunneling microscopy, X-ray magnetic circular dichroism, and density functional theory. We find that each of the Co ions has an orbital moment comparable to that of the spin, leading to magnetic anisotropy, with the spins preferentially oriented along the Co-Co axis. The orbital moment and the associated magnetic anisotropy is tuned by varying the electronic coupling of the molecule to the substrate and the microscope tip. These findings show the need to consider the orbital moment even in systems with strong ligand fields. As a consequence, the description of S = 1/2 ions becomes strongly modified, which have important consequences for these prototypical systems for quantum operations.

Surgical Metastasectomy for Visceral and Bone Prostate Cancer Metastases: A Mini-Review.

Despite growing interest in metastasis-directed therapy (MDT) for prostate cancer (PCa), little is known regarding the feasibility and effectiveness of surgical metastasectomy for isolated lesions. We performed a narrative review of the available evidence supporting metastasectomy for M1b-c lesions in men diagnosed with oligometastatic or oligorecurrent PCa. The case series and case reports we identified indicate that surgical MDT is a safe and feasible treatment option for well-selected patients with a small number of PCa metastases diagnosed via molecular imaging. It is difficult to draw evidence-based conclusions regarding the survival benefit of metastasectomy; however, metastasectomy might lead to a prostate-specific antigen response and could potentially delay systemic therapy in patients with oligometastatic PCa. Prospective studies incorporating novel imaging are needed to better establish the role of metastasectomy for patients with metastatic PCa. PATIENT SUMMARY: We reviewed the evidence on surgical removal of prostate cancer lesions that have spread to the organs (eg, liver and lung) or bone, which are called metastases. Limited results show that this approach is feasible and has favorable outcomes in selected patients.

Spin Crossover in a Cobalt Complex on Ag(111).

The Co-based complex [Co(H2 B(pz)(pypz))2 ] (py=pyridine, pz=pyrazole) deposited on Ag(111) was investigated with scanning tunneling microscopy at ≈5 K. Due to a bis(tridentate) coordination sphere the molecules aggregate mainly into tetramers. Individual complexes in these tetramers undergo reversible transitions between two states with characteristic image contrasts when current is passed through them or one of their neighbors. Two molecules exhibit this bistability while the other two molecules are stable. The transition rates vary linearly with the tunneling current and exhibit an intriguing dependence on the bias voltage and its polarity. We interpret the states as being due to S=1 /2 and 3 /2 spin states of the Co2+ complex. The image contrast and the orders-of-magnitude variations of the switching yields can be tentatively understood from the calculated orbital structures of the two spin states, thus providing first insights into the mechanism of electron-induced excited spin-state trapping (ELIESST).

Electron-Induced Spin-Crossover in Self-Assembled Tetramers.

The spin crossover compound Fe(H2B(pyrazole)(pyridylpyrazole))2 was investigated in detail on Ag(111) with scanning tunneling microscopy (STM). A large fraction of the deposited molecules condenses into gridlike tetramers. Two molecules of each tetramer may be converted between two states by current injection. We attribute this effect to a spin transition. This interpretation is supported by control experiments on the analogous, magnetically passive Zn compound that forms virtually identical tetramers but exhibits no switching. The switching yields were studied for various electron energies, and the resulting values exceed those reported from other SCO systems by 2 orders of magnitude. The other two molecules of a tetramer were immutable. However, they may be used as contacts for current injection that leads to conversion of one of their neighbors. This "remote" switching is fairly efficient with yields reduced by only one to two orders of magnitude compared to direct excitation of a switchable molecule. We present a model of the tetramer structure that reproduces key observations from the experiments. In particular, sterical blocking prevents spin crossover of two molecules of a tetramer. Density functional theory calculations show that the model indeed represents a minimum energy structure. They also reproduce STM images and corroborate a remote-switching mechanism that is based on electron transfer between molecules.

Inducing and Controlling Molecular Magnetism through Supramolecular Manipulation.

Diamagnetic H2 phthalocyanine molecules are probed on superconducting Pb(100) using a low-temperature scanning tunneling micoscope (STM). In supramolecular arrays made with the STM, the molecules acquire a spin as detected via the emergence of Yu-Shiba-Rusinov resonances. The spin moments vary among the molecules and are determined by the electrostatic field that results from polar bonds in the surrounding Pc molecules. The moments are further finely tuned by repositioning the hydrogen atoms of the inner macrocycle of the surrounding molecules.

Iron in a Cage: Fixation of a Fe(II)tpy2 Complex by Fourfold Interlinking.

The coordination sphere of the Fe(II) terpyridine complex 1 is rigidified by fourfold interlinking of both terpyridine ligands. Profiting from an octa-aldehyde precursor complex, the ideal dimensions of the interlinking structures are determined by reversible Schiff-base formation, before irreversible Wittig olefination provided the rigidified complex. Reversed-phase HPLC enables the isolation of the all-trans isomer of the Fe(II) terpyridine complex 1, which is fully characterized. While temperature independent low-spin states were recorded with superconducting quantum interference device (SQUID) measurements for both, the open precursor 8 and the interlinked complex 1, evidence of the increased rigidity of the ligand sphere in 1 was provided by proton T2 relaxation NMR experiments. The ligand sphere fixation in the macrocyclized complex 1 even reaches a level resisting substantial deformation upon deposition on an Au(111) surface, as demonstrated by its pristine form in a low temperature ultra-high vacuum scanning tunneling microscope experiment.

Coverage-Controlled Superstructures of C3 -Symmetric Molecules: Honeycomb versus Hexagonal Tiling.

The competition between honeycomb and hexagonal tiling of molecular units can lead to large honeycomb superstructures on surfaces. Such superstructures exhibit pores that may be used as 2D templates for functional guest molecules. Honeycomb superstructures of molecules that comprise a C3 symmetric platform on Au(111) and Ag(111) surfaces are presented. The superstructures cover nearly mesoscopic areas with unit cells containing up to 3000 molecules, more than an order of magnitude larger than previously reported. The unit cell size may be controlled by the coverage. A fairly general model was developed to describe the energetics of honeycomb superstructures built from C3 symmetric units. Based on three parameters that characterize two competing bonding arrangements, the model is consistent with the present experimental data and also reproduces various published results. The model identifies the relevant driving force, mostly related to geometric aspects, of the pattern formation.

Rotation of Ethoxy and Ethyl Moieties on a Molecular Platform on Au(111).

Molecular rotors have attracted considerable interest for their prospects in nanotechnology. However, their adsorption on supporting substrates, where they may be addressed individually, usually modifies their properties. Here, we investigate the switching of two closely related three-state rotors mounted on platforms on Au(111) using low-temperature scanning tunneling microscopy and density functional theory calculations. Being physisorbed, the platforms retain important gas-phase properties of the rotor. This simplifies a detailed analysis and permits, for instance, the identification of the vibrational modes involved in the rotation process. The symmetry provided by the platform enables active control of the rotation direction through electrostatic interactions with the tip and charged neighboring adsorbates. The present investigation of two model systems may turn out useful for designing platforms that provide directional rotation and for transferring more sophisticated molecular machines from the gas phase to surfaces.

Reversible coordination-induced spin-state switching in complexes on metal surfaces.

Molecular spin switches are attractive candidates for controlling the spin polarization developing at the interface between molecules and magnetic metal surfaces1,2, which is relevant for molecular spintronics devices3-5. However, so far, intrinsic spin switches such as spin-crossover complexes have suffered from fragmentation or loss of functionality following adsorption on metal surfaces, with rare exceptions6-9. Robust metal-organic platforms, on the other hand, rely on external axial ligands to induce spin switching10-14. Here we integrate a spin switching functionality into robust complexes, relying on the mechanical movement of an axial ligand strapped to the porphyrin ring. Reversible interlocked switching of spin and coordination, induced by electron injection, is demonstrated on Ag(111) for this class of compounds. The stability of the two spin and coordination states of the molecules exceeds days at 4 K. The potential applications of this switching concept go beyond the spin functionality, and may turn out to be useful for controlling the catalytic activity of surfaces15.

Spin in a Closed-Shell Organic Molecule on a Metal Substrate Generated by a Sigmatropic Reaction.

Inert metal surfaces present more chances of hosting organic intact radicals than other substrates, but large amounts of delocalized electronic states favor charge transfer and thus spin quenching. Lowering the molecule-substrate interaction is a usual strategy to stabilize radicals on surfaces. In some works, thin insulating layers were introduced to provide a controllable degree of electronic decoupling. Recently, retinoid molecules adsorbed on gold have been manipulated with a scanning tunneling microscope (STM) to exhibit a localized spin, but calculations failed to find a radical derivative of the molecule on the surface. Now the formation of a neutral radical spatially localized in a tilted and lifted cyclic end of the molecule is presented. An allene moiety provokes a perpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated allene in its lifted subpart. DFT calculations and STM manipulations give support to the proposed mechanism.

The Kondo resonance line shape in scanning tunnelling spectroscopy: instrumental aspects.

In the scanning tunnelling microscope, the many-body Kondo effect leads to a zero-bias feature of the differential conductance spectra of magnetic adsorbates on surfaces. The intrinsic line shape of this Kondo resonance and its temperature dependence in principle contain valuable information. We use measurements on a molecular Kondo system, all- trans retinoic acid on Au(1 1 1), and model calculations to discuss the role of instrumental broadening. The modulation voltage used for the lock-in detection, noise on the sample voltage, and the temperature of the microscope tip are considered. These sources of broadening affect the apparent line shapes and render difficult a determination of the intrinsic line width, in particular when variable temperatures are involved.

Disentangling Magnetic Hardening and Molecular Spin Chain Contributions to Exchange Bias in Ferromagnet/Molecule Bilayers.

We performed ferromagnetic resonance and magnetometry experiments to clarify the relationship between two reported magnetic exchange effects arising from interfacial spin-polarized charge transfer in ferromagnetic metal (FM)/molecule bilayers: the magnetic hardening effect and spinterface-stabilized molecular spin chains. To disentangle these effects, we tuned the metal phthalocyanine molecule central site's magnetic moment to enhance or suppress the formation of spin chains in the molecular film. We find that both effects are distinct, and additive. In the process, we extend the list of FM/molecule candidate pairs that are known to generate magnetic exchange effects, experimentally confirm the predicted increase in anisotropy upon molecular adsorption, and show that spin chains within the molecular film can enhance magnetic exchange. Our results confirm, as an echo to progress regarding inorganic spintronic tunnelling, that spintronic tunnelling across structurally ordered organic barriers has been reached through previous magnetotransport experiments.

Light-Induced Spin Crossover in an Fe(II) Low-Spin Complex Enabled by Surface Adsorption.

Understanding and controlling the spin-crossover properties of molecular complexes can be of particular interest for potential applications in molecular spintronics. Using near-edge X-ray absorption fine structure spectroscopy, we investigated these properties for a new vacuum-evaporable Fe(II) complex, namely [Fe(pypyr(CF3)2)2(phen)] (pypyr = 2-(2'-pyridyl)pyrrolide, phen = 1,10-phenanthroline). We find that the spin-transition temperature, well above room temperature for the bulk compound, is drastically lowered for molecules arranged in thin films. Furthermore, while within the experimentally accessible temperature range (2 K < T < 410 K) the bulk material shows indication of neither light-induced excited spin-state trapping nor soft X-ray-induced excited spin-state trapping, these effects are observed for molecules within thin films up to temperatures around 100 K. Thus, by arranging the molecules into thin films, a nominal low-spin complex is effectively transformed into a spin-crossover complex.

Scale-Up of Innovative Honeycomb Reactors for Power-to-Gas Applications - The Project Store&Go.

The German "Energiewende" is heavily based on electric power and, therefore, requests solutions to serve non-electric energy uses and to store electric energy in large scale. Synthetic natural gas (SNG) produced with hydrogen from water electrolysis and with CO2 from mainly renewable sources is one approach. For the catalytic SNG production efficient removal and utilization of the reaction heat is the main issue. A metallic honeycomb-like carrier-based reactor proved in laboratory scale to match this challenge. This type of reactor shows good heat conductivity and enables optimized operation. In the EU-funded project Store&Go the honeycomb methanation is scaled up to MW-scale. For this, heat transfer and kinetic data were determined experimentally and used in CFD calculations for the reactor design. Finally a SNG plant with 1 MW feed-in will be built and fully integrated operation will be shown.

Robust and Selective Switching of an FeIII Spin-Crossover Compound on Cu2N/Cu(100) with Memristance Behavior.

The switching between two spin states makes spin-crossover molecules on surfaces very attractive for potential applications in molecular spintronics. Using scanning tunneling microscopy, the successful deposition of [Fe(pap)2]+ (pap = N-2-pyridylmethylidene-2-hydroxyphenylaminato) molecules on Cu2N/Cu(100) surface is evidenced. The deposited FeIII spin-crossover compound is controllably switched between three different states, each of them exhibiting a characteristic tunneling conductance. The conductance is therefore employed to readily read the state of the molecules. A comparison of the experimental data with the results of density functional theory calculations reveals that all Fe(pap)2 molecules are initially in their high-spin state. The two other states are compatible with the low-spin state of the molecule but differ with respect to their coupling to the substrate. As a proof of concept, the reversible and selective nature of the switching is used to build a two-molecule memory.

Ligand-Induced Energy Shift and Localization of Kondo Resonances in Cobalt-Based Complexes on Cu(111).

Magnetic sandwich complexes are of particular interest for molecular spintronics. Using scanning tunneling microscopy, we evidence the successful deposition of 1,3,5-tris(η6-borabenzene-η5-cyclopentadienylcobalt) benzene, a molecule composed of three connected magnetic sandwich units, on Cu(111). Scanning tunneling spectra reveal two distinct spatial-dependent narrow resonances close to the Fermi level for the trimer molecules as well as for molecular fragments composed of one and two magnetic units. With the help of density functional theory, these resonances are interpreted as two Kondo resonances originating from two distinct nondegenerate d-like orbitals. These Kondo resonances are found to have defined spatial extents dictated by the hybridization of the involved orbitals with that of the ligands. These results opens promising perspectives for investigating complex Kondo systems composed of several "Kondo" orbitals.