搜索结果：Organometallics

We present an investigation of one-photon valence-shell photoelectron spectroscopy and photoelectron circular dichroism (PECD) for the chiral molecule (1R,4R)-3-(heptafluorobutyryl)-(+)-camphor (HFC) and its europium complex Eu(III) tris[3-(heptafluorobutyryl)-(1R,4R)-camphorate] (Eu-HFC$_{3}$), the latter of which constitutes the heaviest organometallic molecule for which PECD has yet been measured. We discuss the role of keto-enol tautomerism in HFC, both as a free molecule and complexed in Eu-HFC$_{3}$. PECD is a uniquely sensitive probe of molecular chirality and structure such as absolute configuration, conformation, isomerisation, and substitution, and as such is in principle well suited to unambiguously resolving tautomers; however modeling remains challenging. For small organic molecules, theory is generally capable of accounting for experimentally measured PECD asymmetries, but significantly poorer agreement is typically achieved for the case of large open-shell systems. Here, we report PECD asymmetries ranging up to $\sim8\%$ for HFC and $\sim7\%$ for Eu-HFC$_{3}$, of similar magnitude to those reported previously for smaller isolated chiral molecules, indicating that PEC

Ti-based two-dimensional transition-metal carbides (MXenes) have attracted attention due to their superior properties and are being explored across various applications1,2. Despite their versatile properties, superconductivity has never been demonstrated, not even predicted, for this important group of 2D materials. In this work, we have introduced an electrochemical intercalation protocol to construct versatile organometallic-inorganic hybrid MXenes and achieved tunable superconductivity in the metallocene-modified layered crystals. Through structural editing of MXene matrix at atomic scale and meticulously modulated intercalation route, Ti3C2Tx intercalated with metallocene species exhibits a superconductive transition temperature (Tc) of 10.2 K. Guest intercalation induced electron filling and strain engineering are responsible for the emerging superconductivity in this intrinsically non-superconducting material. Theoretically, simulated electron-phonon interaction effects further elucidate the nature of the changes in Tc. Furthermore, the Tc of crafted artificial superlattices beyond Ti-based MXenes have been predicted, offering a general strategy for engineering superconductiv

Control of individual spins at the atomic level holds great promise for miniaturized spintronics, quantum sensing, and quantum information processing. Both single atomic and molecular spin centers are prime candidates for these applications and are often individually addressed and manipulated using scanning tunneling microscopy (STM). In this work, we present a hybrid approach and demonstrate a robust method for self-assembly of magnetic organometallic complexes consisting of individual iron (Fe) atoms and molecules on a silver substrate using STM. We employ two types of molecules, bis(dibenzoylmethane) copper(II) [Cu(dbm)2] and iron phthalocyanine (FePc). We show that in both cases the Fe atoms preferentially attach underneath the benzene ring ligand of the molecules, effectively forming an organometallic half-sandwich arene complex, Fe(C6H6), that is akin to the properties of metallocenes. In both situations, a molecule can be combined with up to two Fe atoms. In addition, we observe a change in the magnetic properties of the attached Fe atoms in scanning tunneling spectroscopy, revealing a distinct Kondo signature at the Fe sites. We explain the latter using density functional t

This thesis investigates the mechanically controlled break junctions, with a particular emphasis on elucidating the behaviour of molecular currents at room temperature. The core of this experimental investigation involves a detailed analysis of conductance, examining how it varies over time and with changes in the gap between electrodes. Additionally, this study thoroughly evaluates transmission properties, coupling effects, and current characteristics. A pivotal aspect of the research was the meticulous current measurement, followed by carefully selecting optimal data sets. This process set the stage for an in-depth analysis of resonant tunnelling phenomena observed through a single channel. Notably, these experiments were conducted under open atmospheric conditions at room temperature. A significant finding from this study is the recognition that our current model requires refinement. This adjustment is necessary to encapsulate a broader spectrum of molecular transport mechanisms more accurately. Furthermore, this work significantly advances our comprehension of quantum effects in single-molecule junctions, particularly concerning similar molecules to Corannulene extending to som

Understanding electrical characteristics and corresponding transport models at single molecular junctions is crucial. There have been many reports on organic compounds-based single molecular junctions. However, organometallic compounds-based single molecular junctions have not been explored yet. Re(I) organometallic compounds are known to exhibit intriguing photophysical properties scrutinized for photocatalysis, and light-emitting diodes but have not been explored in molecular electronics. In this work, a theoretical model study on the I-V characteristics of two Re(I)-carbonyl complexes bearing Re-P and Re-N-N linkage has been meticulously chosen. Tunneling and hopping transport in Au/Re(I)-complex/Au single-molecule junctions are governed by Landauer-formalism and the Marcus theory, respectively. Interestingly, variations in molecular architecture culminate in notable variations in junction functionality and mechanism of charge conduction. Physical parameters influencing the device characteristics such as dipole moment, molecule-electrode coupling strength, voltage division factor, and temperature have been extensively studied which offers modulation of the characteristics and de

Graphdiyne-based carbon systems generate intriguing layered sp-sp$^2$ organometallic lattices, characterized by flexible acetylenic groups connecting planar carbon units through metal centers. At their thinnest limit, they can result in two-dimensional (2D) organometallic networks exhibiting unique quantum properties and even confining the surface states of the substrate, which is of great importance for fundamental studies. In this work, we present the on-surface synthesis of a highly crystalline 2D organometallic network grown on Ag(111). The electronic structure of this mixed honeycomb-kagome arrangement - investigated by angle-resolved photoemission spectroscopy and scanning tunneling spectroscopy - reveals a strong electronic conjugation within the network, leading to the formation of two intense electronic band-manifolds. In comparison to theoretical density functional theory calculations, we observe that these bands exhibit a well-defined orbital character that can be associated with distinct regions of the sp-sp$^2$ monomers. Moreover, we find that the halogen by-products resulting from the network formation locally affect the pore-confined states, causing a significant ene

We demonstrate the fabrication of sharp nanopillars of high aspect ratio onto specialized atomic force microscopy (AFM) microcantilevers and their use for high-speed AFM of DNA and nucleoproteins in liquid. The fabrication technique uses localized charged-particle-induced deposition with either a focused beam of helium ions or electrons in a helium ion microscope (HIM) or scanning electron microscope (SEM). This approach enables customized growth onto delicate substrates with nanometer-scale placement precision and in-situ imaging of the final tip structures using the HIM or SEM. Tip radii of <10 nm are obtained and the underlying microcantilever remains intact. Instead of the more commonly used organic precursors employed for bio-AFM applications, we use an organometallic precursor (tungsten hexacarbonyl) resulting in tungsten-containing tips. Transmission electron microscopy reveals a thin layer of carbon on the tips. Consequently, the interaction of the new tips with biological specimens is likely very similar to that of standard carbonaceous tips, with the added benefit of robustness. A further advantage of the organometallic tips is that compared to carbonaceous tips they b

Selective activation and controlled functionalization of C-H bonds in organic molecules is one of the most desirable processes in synthetic chemistry. Despite progress in heterogeneous catalysis using metal surfaces, this goal remains challenging due to the stability of C-H bonds and their ubiquity in precursor molecules, hampering regioselectivity. Here, we examine the interaction between 9,10-dicyanoanthracene (DCA) molecules and Au adatoms on a Ag(111) surface at room temperature (RT). Characterization via low-temperature scanning tunneling microscopy, spectroscopy, and noncontact atomic force microscopy, supported by theoretical calculations, revealed the formation of organometallic DCA-Au-DCA dimers, where C atoms at the ends of the anthracene moieties are bonded covalently to single Au atoms. The formation of this organometallic compound is initiated by a regioselective cleaving of C-H bonds at RT. Hybrid quantum mechanics/molecular mechanics calculations show that this regioselective C-H bond cleaving is enabled by an intermediate metal-organic complex which significantly reduces the dissociation barrier of a specific C-H bond. Harnessing the catalytic activity of single met

We present the results of first-principle calculations using the Vienna Ab-initio Simulation Package (VASP) for a new class of organometallics labeled TM3C6O6 (TM =Sc, Ti, V, Cr, Fe, Co, Ni and Cu) in the form of planar, two-dimensional, periodic free-standing layers. These materials, which can be produced by on-surface coordination on metallic surfaces, have a kagome lattice of TM ions. Calculating the structural properties, we show that all considered materials have local magnetic moments in the ground state, but four of them (with Fe, Co, Ni and Cu) show spin-crossover behavior by changing the lattice constant, which could be valuable for possible epitaxy routes on various substrates. Surprisingly, we find a very large richness of electronic and magnetic properties, qualifying these materials as highly promising metal-organic topological quantum materials. We find semi-conductors with nearest-neighbor ferromagnetic (FM) or antiferromagnetic (AFM) couplings for V, and Sc and Cr, respectively, being of potential interest to study spin ice or spin liquids on the 2D kagome lattice. Other TM ion systems combine AFM couplings with metallic behavior (Ti, Fe and Ni) or are ferromagnetic

Organometallic lead halide perovskites are highly efficient materials for solar cells and other optoelectronic applications due to their high quantum efficiency and exceptional semiconducting properties. A peculiarity of these perovskites is the substantial ionic motion under external forces. Here, we reveal that electric field-and light-induced ionic motion in MAPbX3 crystals (X=Cl, Br, I and MA=CH3NH3) leads to unexpected piezoelectric-like response, an order of magnitude larger than in ferroelectric perovskite oxides. The nominal macroscopic symmetry of the crystals is broken by redistribution of ionic species, which can be controlled deterministically by light and electric field. The revealed piezoelectric response is possibly present in other materials with significant ionic activity but the unique feature of organometallic perovskites is the strong effect on the piezoelectric response of interplay of ionic motion (MA+ and X-1) and photoelectrons generated with illumination.

A colossal ancient collision may have left some of the Moon’s deepest secrets surprisingly close to future Artemis landing sites。 By recreating the impact that formed the giant South Pole-Aitken basin—the Moon’s largest and oldest crater—scientists found that a low-angle strike from a large, iron-cored object blasted material from deep inside the M

Deep beneath the ground in China, the massive JUNO neutrino observatory has delivered its first major scientific breakthrough, achieving one of the most precise measurements yet of how elusive neutrinos change as they travel。 Using just 59 days of data, researchers sharply improved measurements of key neutrino properties, boosting confidence that J

A new study suggests Earth may have been sending tiny hitchhikers to Venus for billions of years。 Researchers found that asteroid impacts could launch microbes into space, where some might survive the journey and end up suspended in Venus' clouds。 If future missions detect life there, there's a surprising chance it didn't originate on Venus at all—

A newly proposed quantum sensing technique could make it much easier to identify one of physics’ newest and most intriguing classes of magnets: altermagnets。 These unusual materials, discovered only a few years ago, appear to combine the speed and efficiency of antiferromagnets with some of the useful electronic properties of traditional magnets, m

Astronomers may be closing in on a long-standing cosmic mystery: why some of the universe’s biggest galaxies seem to have far fewer stars than expected。 Using NASA- and JAXA-supported XRISM observations of a galaxy called NGC 4151, researchers found strong evidence that supermassive black holes can unleash powerful winds that blow away the raw mate

Rock weathering may release or draw down carbon dioxide—it depends on the rock

Scientists at RIKEN have proposed a new way to make quantum systems synchronize in only one direction—like a one-way street for sound particles known as phonons。 The breakthrough combines two quantum effects to create a form of one-way quantum synchronization that remains surprisingly stable even when exposed to manufacturing flaws and environmenta

The global cobalt supply chain is more interconnected—and more vulnerable—than previously thought, with disruptions capable of triggering far-reaching cascades across multiple countries and industries。 Researchers warn that protecting battery supply chains will require system-wide coordination because critical bottlenecks can turn local shocks into

Oxford physicists have created an entirely new type of Schrödinger’s cat-like quantum state using components that are themselves highly quantum in nature。 The advance could open new possibilities for more resilient quantum computers and deeper insights into the strange rules that govern the quantum universe