Spin crossover in dinuclear iron(II) complexes bridged by bis-bipyridine ligands: dimer effects on electronic structure, spectroscopic properties and spin-state switching.

Inspired by the well-studied mononuclear spin crossover compound [Fe(H2B(pz)2)2(bipy)], the bipyridine-based bisbidentate ligands 1,2-di(2,2'-bipyridin-5-yl)ethyne (ac(bipy)2) and 1,4-di(2,2'-bipyridine-5-yl)-3,5-dimethoxybenzene (Ph(OMe)2(bipy)2) are used to bridge two [Fe(H2B(pz)2)2] units, leading to the charge-neutral dinuclear iron(II) compounds [{Fe(H2B(pz)2)2}2 µ-(ac(bipy)2)] (1) and [{Fe(H2B(pz)2)2}2 µ-(Ph(OMe)2(bipy)2)] (2), respectively. The spin-crossover properties of these molecules are investigated by temperature-dependent PPMS measurements, Mössbauer, vibrational and UV/Vis spectroscopy as well as X-ray absorption spectroscopy. While compound 1 undergoes complete SCO with T1/2 = 125 K, an incomplete spin transition is observed for 2 with an inflection point at 152 K and a remaining high-spin fraction of 40% below 65 K. The spin transitions of the dinuclear compounds are also more gradual than for the parent compound [Fe(H2B(pz)2)2(bipy)]. This is attributed to steric hindrance between the molecules, limiting intermolecular interactions such as π-π-stacking.

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.

On-Surface Design of a 2D Cobalt-Organic Network Preserving Large Orbital Magnetic Moment.

The design of antiferromagnetic nanomaterials preserving large orbital magnetic moments is important to protect their functionalities against magnetic perturbations. Here, we exploit an archetype H6HOTP species for conductive metal-organic frameworks to design a Co-HOTP one-atom-thick metal-organic architecture on a Au(111) surface. Our multidisciplinary scanning probe microscopy, X-ray absorption spectroscopy, X-ray linear dichroism, and X-ray magnetic circular dichroism study, combined with density functional theory simulations, reveals the formation of a unique network design based on threefold Co+2 coordination with deprotonated ligands, which displays a large orbital magnetic moment with an orbital to effective spin moment ratio of 0.8, an in-plane easy axis of magnetization, and large magnetic anisotropy. Our simulations suggest an antiferromagnetic ground state, which is compatible with the experimental findings. Such a Co-HOTP metal-organic network exemplifies how on-surface chemistry can enable the design of field-robust antiferromagnetic materials.

Influence of magnetic domain walls on all-optical magnetic toggle switching in a ferrimagnetic GdFe film.

We present a microscopic magnetic domain imaging study of single-shot all-optical magnetic toggle switching of a ferrimagnetic Gd26Fe74 film with out-of-plane easy axis of magnetization by X-ray magnetic circular dichroism photoelectron emission microscopy. Individual linearly polarized laser pulses of 800 nm wavelength and 100 fs duration above a certain threshold fluence reverse the sample magnetization, independent of the magnetization direction, the so-called toggle switching. Local deviations from this deterministic behavior close to magnetic domain walls are studied in detail. Reasons for nondeterministic toggle switching are related to extrinsic effects, caused by pulse-to-pulse variations of the exciting laser system, and to intrinsic effects related to the magnetic domain structure of the sample. The latter are, on the one hand, caused by magnetic domain wall elasticity, which leads to a reduction of the domain-wall length at features with sharp tips. These features appear after the optical switching at positions where the line of constant threshold fluence in the Gaussian footprint of the laser pulse comes close to an already existing domain wall. On the other hand, we identify the presence of laser-induced domain-wall motion in the toggle-switching event as a further cause for local deviations from purely deterministic toggle switching.

Tuning the Magnetic Anisotropy of Lanthanides on a Metal Substrate by Metal-Organic Coordination.

Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy-carboxylate metal-organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X-ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface-supported metal-organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in-plane easy magnetization axis despite the out-of-plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal-organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces.

Spin-Crossover Molecules on Surfaces: From Isolated Molecules to Ultrathin Films.

Molecular spintronics seeks to use single or few molecules as functional building blocks for spintronic applications, directly relying on molecular properties or properties of interfaces between molecules and inorganic electrodes. Spin-crossover molecules (SCMs) are one of the most promising classes of candidates for molecular spintronics due to their bistability deriving from the existence of two spin states that can be reversibly switched by temperature, light, electric fields, etc. Building devices based on single or few molecules would entail connecting the molecule(s) with solid surfaces and understanding the fundamental behavior of the resulting assemblies. Herein, the investigations of SCMs on solid surfaces, ranging from isolated single molecules (submonolayers) to ultrathin films (mainly in the sub-10 nm range) are summarized. The achievements, challenges and prospects in this field are highlighted.

Surface-orientation- and ligand-dependent quenching of the spin magnetic moment of Co porphyrins adsorbed on Cu substrates.

Porphyrin molecules are particularly interesting candidates for spintronic applications due to their bonding flexibility, which allows to modify their properties substantially by the addition or transformation of ligands. Here, we investigate the electronic and magnetic properties of cobalt octaethylporphyrin (CoOEP), deposited on copper substrates with two distinct crystallographic surface orientations, Cu(100) and Cu(111), with X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD). A significant magnetic moment is present in the Co ions of the molecules deposited on Cu(100), but it is completely quenched on Cu(111). Heating the molecules on both substrates to 500 K induces a ring-closure reaction with cobalt tetrabenzoporphyrin (CoTBP) as reaction product. In these molecules, the magnetic moment is quenched on both surfaces. Our XMCD and XAS measurements suggest that the filling of the dz2 orbital leads to a non-integer valence state and causes the quench of the spin moments on all samples except CoOEP/Cu(100), where the molecular conformation induces variations to the ligand field that lift the quench. We further employ density functional theory calculations, supplemented with on-site Coulomb correlations (DFT+U), to study the adsorption of these spin-bearing molecules on the Cu substrates. Our calculations show that charge transfer from the Cu substrates as well as charge redistribution within the Co 3d orbitals lead to the filling of the Co minority spin dz2 orbital, causing a 'turning off' of the exchange splitting and quenching of the spin moment at the Co magnetic centers. Our investigations suggest that, by this mechanism, molecule-substrate interactions can be used to control the quenching of the magnetic moments of the adsorbed molecules.

Effect of ligand methylation on the spin-switching properties of surface-supported spin-crossover molecules.

X-ray absorption spectroscopy investigations of the spin-state switching of spin-crossover (SCO) complexes adsorbed on a highly-oriented pyrolytic graphite (HOPG) surface have shown so far that HOPG is a promising candidate to realize applications such as spintronic devices because of the stability of SCO complexes on HOPG and the possibility of highly efficient thermal and light-induced spin-state switching. Herein, we present the spin switching of several Fe(II) SCO complexes adsorbed on an HOPG surface with particular emphasis on the thermally induced spin transition behaviour with respect to different structural modifications. The complexes of the type [Fe(bpz)2(L)] (bpz = dihydrobis(pyrazolyl)borate, L = 1,10-phenanthroline, 2,2'-bipyridine) and their methylated derivatives exhibit SCO in the solid state with some differences regarding cooperative effects. However, in the vacuum-deposited thick films on quartz, complete and more gradual spin transition behavior is observable via UV/vis spectroscopy. In contrast to that, all complexes show large differences upon direct contact with HOPG. Whereas the unmodified complexes show thermal and light-induced SCO, the addition of e.g. two or four methyl groups leads to a partial or a complete loss of the SCO on the surface. The angle-dependent measurement of the N K-edge compared to calculations indicates that the complete SCO and HS-locked molecules on the surface exhibit a similar preferential orientation, whereas complexes undergoing an incomplete SCO exhibit a random orientation on the surface. These results are discussed in the light of molecule-substrate interactions.

Coupling of pinned magnetic moments in an antiferromagnet to a ferromagnet and its role for exchange bias.

The interaction between uncompensated pinned magnetic moments within an antiferromagnetic (AFM) layer and an adjacent ferromagnetic (FM) layer responsible for the existence of exchange bias is explored in epitaxially grown trilayers of the form FM2/AFM/FM1 on Cu3Au(0 0 1) where FM1 is ~12 atomic monolayers (ML) Ni, FM2 is 21-25 ML Ni, and AFM is 27 ML or 50 ML Ni~25Mn~75. Field cooling for parallel or antiparallel alignment of the out-of-plane magnetizations of the two FM layers does not make a difference for the temperature-dependent coercivity (H C), magnitude of exchange bias field (H eb), AFM ordering temperature (T AFM), and blocking temperature for exchange bias (T b). We explain this by a model in which the uncompensated pinned magnetic moments distributed within the volume of the AFM layer interact with both of the FM layers, albeit with different strength. Parallel and antiparallel coupling between the magnetization of the pinned moments and the FM layers equally exists. This leads to the experimentally observed independence of H C, H eb, as well as of T AFM and T b on the magnetization direction of the FM layers during field cooling. These results provide new and detailed insight into revealing the subtle and complex nature of the exchange bias effect.

Europium Cyclooctatetraene Nanowire Carpets: A Low-Dimensional, Organometallic, and Ferromagnetic Insulator.

We investigate the magnetic and electronic properties of europium cyclooctatetraene (EuCot) nanowires by means of low-temperature X-ray magnetic circular dichroism (XMCD) and scanning tunneling microscopy (STM) and spectroscopy (STS). The EuCot nanowires are prepared in situ on a graphene surface. STS measurements identify EuCot as an insulator with a minority band gap of 2.3 eV. By means of Eu M5,4 edge XMCD, orbital and spin magnetic moments of (-0.1 ± 0.3)µB and (+7.0 ± 0.6)µB, respectively, were determined. Field-dependent measurements of the XMCD signal at the Eu M5 edge show hysteresis for grazing X-ray incidence at 5 K, thus confirming EuCot as a ferromagnetic material. Our density functional theory calculations reproduce the experimentally observed minority band gap. Modeling the experimental results theoretically, we find that the effective interatomic exchange interaction between Eu atoms is on the order of millielectronvolts, that magnetocrystalline anisotropy energy is roughly half as big, and that dipolar energy is approximately ten times lower.

Evolution of cooperativity in the spin transition of an iron(II) complex on a graphite surface.

Cooperative effects determine the spin-state bistability of spin-crossover molecules (SCMs). Herein, the ultimate scale limit at which cooperative spin switching becomes effective is investigated in a complex [Fe(H2B(pz)2)2(bipy)] deposited on a highly oriented pyrolytic graphite surface, using x-ray absorption spectroscopy. This system exhibits a complete thermal- and light-induced spin transition at thicknesses ranging from submonolayers to multilayers. On increasing the coverage from 0.35(4) to 10(1) monolayers, the width of the temperature-induced spin transition curve narrows significantly, evidencing the buildup of cooperative effects. While the molecules at the submonolayers exhibit an apparent anticooperative behavior, the multilayers starting from a double-layer exhibit a distinctly cooperative spin switching, with a free-molecule-like behavior indicated at around a monolayer. These observations will serve as useful guidelines in designing SCM-based devices.

Optical differential reflectance spectroscopy for photochromic molecules on solid surfaces.

Optical reflectance of thin adsorbates on solid surfaces is able to reveal fundamental changes of molecular properties compared to bulk systems. The detection of very small changes in the optical reflectance required several technical improvements in the past decades. We present an experimental setup that is capable of high-quality measurements of submonolayers and ultrathin layers of photochromic molecules on surfaces as well as quantifying their isomerization kinetics. By using photomultipliers as detectors, an enhancement of the signal-to-noise ratio by a factor of three with a total reduction of light exposure on the sample by at least four orders of magnitude is achieved. The potential of the experimental setup is demonstrated by a characterization of the photoswitching and thermal switching of a spirooxazine derivate on a bismuth surface.

Soft-x-ray-induced spin-state switching of an adsorbed Fe(II) spin-crossover complex.

For probing the nature of spin-state switching in spin-crossover molecules adsorbed on surfaces, x-ray absorption spectroscopy has emerged as a powerful tool due to its high sensitivity and element selectivity in tracing even subtle electronic, magnetic, or chemical changes. However, the x-rays itself can induce a spin transition and might have unwanted influence while investigating the effect of other stimuli such as temperature or light, or of the surface, on the spin switching behaviour. Herein, we present the spin switching of an Fe(II) complex adsorbed on a highly oriented pyrolytic graphite surface with particular emphasis on the x-ray-induced switching. For a submonolayer coverage, the complex undergoes a complete and reversible temperature- and light-induced spin transition. The spin states are switched both ways by x-rays at 5 K, i.e. from the high-spin state to the low-spin state or vice versa, depending on the relative amount of each species. Furthermore, we quantify the fraction of molecules undergoing soft x-ray-induced photochemistry, a process which results in an irreversible low-spin state component, for a particular exposure time. This can be greatly suppressed by reducing the beam intensity.

Light-induced photoisomerization of a diarylethene molecular switch on solid surfaces.

Diarylethenes are molecular switches, the state of which can efficiently be controlled by illumination with ultraviolet or visible light. To use the change in the molecular properties when switching between the two states for a specific function, direct contact with solid surfaces is advantageous as it provides immobilization. Here we present a study of a diarylethene derivate (T-DAE, 1,2-bis(5-methyl-2-phenylthiazol-4-yl)cyclopent-1-ene) in direct contact with highly ordered graphite as well as with semimetallic Bi(1 1 1) surfaces by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy and simulated spectra based on density functional theory. On both surfaces, the molecule can be switched from its open to its closed form by 325-475 nm broadband or ultraviolet illumination. On the other hand, back isomerization to the ring-open T-DAE was not possible.

The Importance of Gene-Drug-Drug-Interactions in Pharmacogenomics Decision Support: An Analysis Based on Austrian Claims Data.

While pharmacogenomic testing combined with clinical decision support has the potential to increase the safety and efficacy of medical treatments, the intake of multiple prescription drugs can - if not sufficiently addressed by decision support solutions - impair the effectiveness of such interventions by modulating the capacity of precisely those enzymes whose function pharmacogenomic tests try to predict. We quantified the potential extent of such drug-mediated mismatches between genotype-derived phenotypes and real phenotypes, commonly called "phenoconversion", by screening claims data from 1,587,829 Austrian health insurance holders of the years 2006 and 2007 for concomitant prescriptions of drugs that can be dosed based on pharmacogenomics, and drugs that modulate enzyme activity. In total, 232,398 such prescription overlaps were detected, of which more than half (54.6%) could be attributed to co-prescriptions of moderate or strong modulators. Our results indicate that prescription drug-mediated phenoconversion is not uncommon, and should therefore be adequately reflected in decision support solutions by integrating algorithms to detect potential gene-drug-drug interactions.

Controlling the magnetism of adsorbed metal-organic molecules.

Gaining control on the size or the direction of the magnetic moment of adsorbed metal-organic molecules constitutes an important step towards the realization of a surface-mounted molecular spin electronics. Such control can be gained by taking advantage of interactions of the molecule's magnetic moment with the environment. The paramagnetic moments of adsorbed metal-organic molecules, for example, can be controlled by the interaction with magnetically ordered substrates. Metalloporphyrins and -phthalocyanines display a quasi-planar geometry, allowing the central metal ion to interact with substrate electronic states. This can lead to magnetic coupling with a ferromagnetic or even antiferromagnetic substrate. The molecule-substrate coupling can be mediated and controlled by insertion layers such as oxygen atoms, graphene, or nonmagnetic metal layers. Control on the magnetic properties of adsorbed metalloporphyrins or -phthalocyanines can also be gained by on-surface chemical modification of the molecules. The magnetic moment or the magnetic coupling to ferromagnetic substrates can be changed by adsorption and thermal desorption of small molecules that interact with the fourfold-coordinated metal center via the remaining axial coordination site. Spin-crossover molecules, which possess a metastable spin state that can be switched by external stimuli such as temperature or light, are another promising class of candidates for control of magnetic properties. However, the immobilization of such molecules on a solid surface often results in a quench of the spin transition due to the interaction with the substrate. We present examples of Fe(II) spin-crossover complexes in direct contact with a solid surface that undergo a reversible spin-crossover transition as a function of temperature, by illumination with visible light, or can be switched by the tip of a scanning tunneling microscope.

How Many Patients Could Benefit From Pre-emptive Pharmacogenomic Testing and Decision Support? A Retrospective Study Based on Nationwide Austrian Claims Data.

Pre-emptive pharmacogenetic (PGx) testing combined with clinical decision support is a promising new strategy for making pharmacotherapy safer and more effective. To estimate the number of patients whose therapies could be guided by this approach, we analysed claims data for patients in Austria in the years 2006 and 2007. We calculated the number of patients receiving one or several drugs for with pharmacogenomic guidelines are available (PGx drugs). The cohort consisted of 6,761,034 patients and was split into four age groups. Patients in the age group >= 65 were prescribed the most PGx drugs, with 72% of the patients receiving at least one PGx drug. 39.1% of all people over 65 received at least one drug metabolized by the three most frequent cytochrome P450 enzymes. Our data indicate that a sizable fraction of elderly patients could profit from the implementation of pre-emptive PGx testing and decision support.

Highly Efficient Thermal and Light-Induced Spin-State Switching of an Fe(II) Complex in Direct Contact with a Solid Surface.

Spin crossover (SCO) complexes possess a bistable spin state that reacts sensitively to changes in temperature or excitation with light. These effects have been well investigated in solids and solutions, while technological applications require the immobilization and contacting of the molecules at surfaces, which often results in the suppression of the SCO. We report on the thermal and light-induced SCO of [Fe(bpz)2phen] molecules in direct contact with a highly oriented pyrolytic graphite surface. We are able to switch on the magnetic moment of the molecules by illumination with green light at T = 6 K, and off by increasing the temperature to 65 K. The light-induced switching process is highly efficient leading to a complete spin conversion from the low-spin to the high-spin state within a submonolayer of molecules. [Fe(bpz)2phen] complexes immobilized on weakly interacting graphite substrates are thus promising candidates to realize the vision of an optically controlled molecular logic unit for spintronic devices.