Enhancing activity and selectivity of palladium catalysts in ketone α-arylation by tailoring the imine chelate of pyridinium amidate (PYA) ligands.

Even though α-arylation of ketones is attractive for direct C-H functionalization of organic substrates, the method largely relies on phosphine-ligated palladium complexes. Only recently, efforts have focused on developing nitrogen-based ligands as a more sustainable alternative to phosphines, with pyridine-functionalized pyridinium amidate (pyr-PYA) ,'-bidentate ligands displaying good selectivity and activity. Here, we report on a second generation set of catalyst precursors that feature a 5-membered N-heterocycle instead of a pyridine as chelating unit of the PYA ligand to provide less steric congestion for the rate-limiting transmetalation of the enolate.

Phase shift of coherent magnetization dynamics after ultrafast demagnetization in strongly quenched nickel thin films.

The remagnetization process after ultrafast demagnetization can be described by relaxation mechanisms between the spin, electron, and lattice reservoirs. Thereby, collective spin excitations in form of spin waves and their angular momentum transfer play an important role on the longer timescales. In this work, we address the question whether the magnitude of demagnetization-the so-called quenching-affects the coherency and the phase of the excited spin waves.

Revealing hidden spin polarization in centrosymmetric van der Waals materials on ultrafast timescales.

One of the key challenges for spintronic and quantum technologies is to achieve active control of the spin angular momentum of electrons in nanoscale materials on ultrafast, femtosecond timescales. While conventional ferromagnetic materials and materials supporting spin texture suffer both from conceptional limitations in miniaturization and inefficiency of optical and electronic manipulation, non-magnetic centrosymmetric layered materials with hidden spin polarization may offer an alternative pathway to manipulate the spin degree of freedom by external stimuli. Here we demonstrate an approach for generating transient spin polarization on a femtosecond timescale in the otherwise spin-unpolarized band structure of the centrosymmetric 2H-stacked group VI transition metal dichalcogenide WSe.

Disentangling the multiorbital contributions of excitons by photoemission exciton tomography.

Excitons are realizations of a correlated many-particle wave function, specifically consisting of electrons and holes in an entangled state. Excitons occur widely in semiconductors and are dominant excitations in semiconducting organic and low-dimensional quantum materials. To efficiently harness the strong optical response and high tuneability of excitons in optoelectronics and in energy-transformation processes, access to the full wavefunction of the entangled state is critical, but has so far not been feasible.

Observation of time-reversal symmetry breaking in the band structure of altermagnetic RuO.

Altermagnets are an emerging elementary class of collinear magnets. Unlike ferromagnets, their distinct crystal symmetries inhibit magnetization while, unlike antiferromagnets, they promote strong spin polarization in the band structure. The corresponding unconventional mechanism of time-reversal symmetry breaking without magnetization in the electronic spectra has been regarded as a primary signature of altermagnetism but has not been experimentally visualized to date.

Spin- and angle-resolved photoemission spectroscopy study of heptahelicene layers on Cu(111) surfaces.

It has been demonstrated previously that electrons interact differently with chiral molecules depending on their polarization. For enantiomeric pure monolayers of heptahelicene, opposite asymmetries in spin polarization were reported and attributed to the so-called chirality-induced spin selectivity effect. However, these promising proof-of-concept photoemission experiments lack the angular and energy resolution that could provide the necessary insights into the mechanism of this phenomenon.

Plasmonic wavelength-dependent optical switch.

We design and experimentally demonstrate an optical switch based on the interference of plasmonic modes in whispering gallery mode (WGM) antennas. Simultaneous excitation of even and odd WGM modes, enabled by a small symmetry breaking via non-normal illumination, allows switching the plasmonic near field between opposite sides of the antenna, depending on the excitation wavelength used in a wavelength range of 60 nm centered around 790 nm. This proposed switching mechanism is experimentally demonstrated by combining photoemission electron microscopy (PEEM) with a tunable wavelength femtosecond laser source in the visible and infrared.

Pincer Platinum(II) Hydrides: High Stability Imparted by Donor-Flexible Pyridylidene Amide Ligands and Evidence for Adduct Formation before Protonation.

Donor-flexible ligands are an emerging class of noninnocent ligands. Their ability to adapt their donating strength toward a metal center has had numerous catalytic advantages yet has never been utilized to stabilize and isolate intermediate complexes within these processes. We demonstrate through the use of a pincer ligand containing two donor-flexible pyridylidene amide (PYA) arms in coordination with platinum(II) that this ligand adaptability revealed remarkably stable hydride and formate complexes.

The clinical course of comorbid substance use disorder and attention deficit/hyperactivity disorder: protocol and clinical characteristics of the INCAS study.

Background: Substance use disorders (SUD) often co-occur with attention deficit hyperactivity disorder (ADHD). Although the short-term effects of some specific interventions have been investigated in randomized clinical trials, little is known about the long-term clinical course of treatment-seeking SUD patients with comorbid ADHD.

Aims: This paper presents the protocol and baseline clinical characteristics of the International Naturalistic Cohort Study of ADHD and SUD (INCAS) designed and conducted by the International Collaboration on ADHD and Substance Abuse (ICASA) foundation.

Vectorial Electron Spin Filtering by an All-Chiral Metal-Molecule Heterostructure.

The discovery of the electrons' chiral induced spin selective transmission (CISS) through chiral molecules has opened the pathway for manipulating spin transport in nonmagnetic structures on the nanoscale. CISS has predominantly been explored in structurally helical molecules on surfaces, where the spin selectivity affects only the spin polarization of the electrons along their direction of propagation. Here, we demonstrate a spin selective electron transmission for the point-chiral molecule 3-methylcyclohexanone (3-MCHO) adsorbed on the chiral Cu(643) surface.

Coherent response of the electronic system driven by non-interfering laser pulses.

The strength of light-matter interaction in condensed matter is fundamentally linked to the orientation and oscillation strength of the materials' optical transition dipoles. Structurally anisotropic materials, e.g.

FAIR data enabling new horizons for materials research.

The prosperity and lifestyle of our society are very much governed by achievements in condensed matter physics, chemistry and materials science, because new products for sectors such as energy, the environment, health, mobility and information technology (IT) rely largely on improved or even new materials. Examples include solid-state lighting, touchscreens, batteries, implants, drug delivery and many more. The enormous amount of research data produced every day in these fields represents a gold mine of the twenty-first century.

Energy and Momentum Distribution of Surface Plasmon-Induced Hot Carriers Isolated Spatiotemporal Separation.

Understanding the differences between photon-induced and plasmon-induced hot electrons is essential for the construction of devices for plasmonic energy conversion. The mechanism of the plasmonic enhancement in photochemistry, photocatalysis, and light-harvesting and especially the role of hot carriers is still heavily discussed. The question remains, if plasmon-induced and photon-induced hot carriers are fundamentally different or if plasmonic enhancement is only an effect of field concentration producing these carriers in greater numbers.

Spectroscopic Evidence for a New Type of Surface Resonance at Noble-Metal Surfaces.

We investigated the surface and bulk properties of the pristine (110) surface of silver using threshold photoemission by excitation with light of 5.9 eV. Using a momentum microscope, we identified two distinct transitions along the Γ[over ¯]Y[over ¯] direction of the crystal.

Orbital angular momentum multiplication in plasmonic vortex cavities.

Orbital angular momentum of light is a core feature in photonics. Its confinement to surfaces using plasmonics has unlocked many phenomena and potential applications. Here, we introduce the reflection from structural boundaries as a new degree of freedom to generate and control plasmonic orbital angular momentum.

Mobilization upon Cooling.

Phase transitions between different aggregate states are omnipresent in nature and technology. Conventionally, a crystalline phase melts upon heating as we use ice to cool a drink. Already in 1903, Gustav Tammann speculated about the opposite process, namely melting upon cooling.

The 2021 ultrafast spectroscopic probes of condensed matter roadmap.

In the 60 years since the invention of the laser, the scientific community has developed numerous fields of research based on these bright, coherent light sources, including the areas of imaging, spectroscopy, materials processing and communications. Ultrafast spectroscopy and imaging techniques are at the forefront of research into the light-matter interaction at the shortest times accessible to experiments, ranging from a few attoseconds to nanoseconds. Light pulses provide a crucial probe of the dynamical motion of charges, spins, and atoms on picosecond, femtosecond, and down to attosecond timescales, none of which are accessible even with the fastest electronic devices.

Functional Meta Lenses for Compound Plasmonic Vortex Field Generation and Control.

Surface plasmon polaritons carrying orbital angular momentum are of great fundamental and applied interest. However, common approaches for their generation are restricted to having a weak dependence on the properties of the plasmon-generating illumination, providing a limited degree of control over the amount of delivered orbital angular momentum. Here we experimentally show that by tailoring local and global geometries of vortex generators, a change in helicity of light imposes arbitrary large switching in the delivered plasmonic angular momentum.

Creating a regular array of metal-complexing molecules on an insulator surface at room temperature.

Controlling self-assembled nanostructures on bulk insulators at room temperature is crucial towards the fabrication of future molecular devices, e.g., in the field of nanoelectronics, catalysis and sensor applications.

Ultrafast Charge-Transfer Exciton Dynamics in C Thin Films.

The high flexibility of organic molecules offers great potential for designing the optical properties of optically active materials for the next generation of optoelectronic and photonic applications. However, despite successful implementations of molecular materials in today's display and photovoltaic technology, many fundamental aspects of the light-to-charge conversion in molecular materials have still to be uncovered. Here, we focus on the ultrafast dynamics of optically excited excitons in C thin films depending on the molecular coverage and the light polarization of the optical excitation.

Explicit finite element analysis can predict the mechanical response of conical implant press-fit in homogenized trabecular bone.

Prediction of primary stability is a major challenge in the surgical planning of dental and orthopedic implants. Computational methods become attractive to estimate primary stability from clinical CT images, but implicit finite element analysis of implant press-fit faces convergence issues due to contact and highly distorted elements. This study aims to develop and validate an explicit finite element method to simulate the insertion and primary stability of a rigid implant in a deformable bone while accounting for damage occurring at the bone-implant interface.

Direct evidence for efficient ultrafast charge separation in epitaxial WS/graphene heterostructures.

We use time- and angle-resolved photoemission spectroscopy (tr-ARPES) to investigate ultrafast charge transfer in an epitaxial heterostructure made of monolayer WS and graphene. This heterostructure combines the benefits of a direct-gap semiconductor with strong spin-orbit coupling and strong light-matter interaction with those of a semimetal hosting massless carriers with extremely high mobility and long spin lifetimes. We find that, after photoexcitation at resonance to the A-exciton in WS, the photoexcited holes rapidly transfer into the graphene layer while the photoexcited electrons remain in the WS layer.

Interfacial States Cause Equal Decay of Plasmons and Hot Electrons at Gold-Metal Oxide Interfaces.

We compare the decay of plasmons and "conventional" hot electrons within the same series of gold/metal oxide interfaces. We found an accelerated decay of hot electrons at gold-metal oxide interfaces with decreasing band gap of the oxide material. The decay is accelerated by the increased phase space for electron scattering caused by additional interfacial states.