Two-dimensional heavy fermions in the van der Waals metal CeSiI.

Heavy-fermion metals are prototype systems for observing emergent quantum phases driven by electronic interactions1-6. A long-standing aspiration is the dimensional reduction of these materials to exert control over their quantum phases7-11, which remains a significant challenge because traditional intermetallic heavy-fermion compounds have three-dimensional atomic and electronic structures. Here we report comprehensive thermodynamic and spectroscopic evidence of an antiferromagnetically ordered heavy-fermion ground state in CeSiI, an intermetallic comprising two-dimensional (2D) metallic sheets held together by weak interlayer van der Waals (vdW) interactions. Owing to its vdW nature, CeSiI has a quasi-2D electronic structure, and we can control its physical dimension through exfoliation. The emergence of coherent hybridization of f and conduction electrons at low temperature is supported by the temperature evolution of angle-resolved photoemission and scanning tunnelling spectra near the Fermi level and by heat capacity measurements. Electrical transport measurements on few-layer flakes reveal heavy-fermion behaviour and magnetic order down to the ultra-thin regime. Our work establishes CeSiI and related materials as a unique platform for studying dimensionally confined heavy fermions in bulk crystals and employing 2D device fabrication techniques and vdW heterostructures12 to manipulate the interplay between Kondo screening, magnetic order and proximity effects.

A few-layer covalent network of fullerenes.

The two natural allotropes of carbon, diamond and graphite, are extended networks of sp3-hybridized and sp2-hybridized atoms, respectively1. By mixing different hybridizations and geometries of carbon, one could conceptually construct countless synthetic allotropes. Here we introduce graphullerene, a two-dimensional crystalline polymer of C60 that bridges the gulf between molecular and extended carbon materials. Its constituent fullerene subunits arrange hexagonally in a covalently interconnected molecular sheet. We report charge-neutral, purely carbon-based macroscopic crystals that are large enough to be mechanically exfoliated to produce molecularly thin flakes with clean interfaces-a critical requirement for the creation of heterostructures and optoelectronic devices2. The synthesis entails growing single crystals of layered polymeric (Mg4C60)∞ by chemical vapour transport and subsequently removing the magnesium with dilute acid. We explore the thermal conductivity of this material and find it to be much higher than that of molecular C60, which is a consequence of the in-plane covalent bonding. Furthermore, imaging few-layer graphullerene flakes using transmission electron microscopy and near-field nano-photoluminescence spectroscopy reveals the existence of moiré-like superlattices3. More broadly, the synthesis of extended carbon structures by polymerization of molecular precursors charts a clear path to the systematic design of materials for the construction of two-dimensional heterostructures with tunable optoelectronic properties.

Exciton-coupled coherent magnons in a 2D semiconductor.

The recent discoveries of two-dimensional (2D) magnets1-6 and their stacking into van der Waals structures7-11 have expanded the horizon of 2D phenomena. One exciting application is to exploit coherent magnons12 as energy-efficient information carriers in spintronics and magnonics13,14 or as interconnects in hybrid quantum systems15-17. A particular opportunity arises when a 2D magnet is also a semiconductor, as reported recently for CrSBr (refs. 18-20) and NiPS3 (refs. 21-23) that feature both tightly bound excitons with a large oscillator strength and potentially long-lived coherent magnons owing to the bandgap and spatial confinement. Although magnons and excitons are energetically mismatched by orders of magnitude, their coupling can lead to efficient optical access to spin information. Here we report strong magnon-exciton coupling in the 2D A-type antiferromagnetic semiconductor CrSBr. Coherent magnons launched by above-gap excitation modulate the exciton energies. Time-resolved exciton sensing reveals magnons that can coherently travel beyond seven micrometres, with a coherence time of above five nanoseconds. We observe these exciton-coupled coherent magnons in both even and odd numbers of layers, with and without compensated magnetization, down to the bilayer limit. Given the versatility of van der Waals heterostructures, these coherent 2D magnons may be a basis for optically accessible spintronics, magnonics and quantum interconnects.

CrSBr: An Air-Stable, Two-Dimensional Magnetic Semiconductor.

The discovery of magnetic order at the 2D limit has sparked new exploration of van der Waals magnets for potential use in spintronics, magnonics, and quantum information applications. However, many of these materials feature low magnetic ordering temperatures and poor air stability, limiting their fabrication into practical devices. In this Mini-Review, we present a promising material for fundamental studies and functional use: CrSBr, an air-stable, two-dimensional magnetic semiconductor. Our discussion highlights experimental research on bulk CrSBr, including quasi-1D semiconducting properties, A-type antiferromagnetic order (TN = 132 K), and strong coupling between its electronic and magnetic properties. We then discuss the behavior of monolayer and few-layer flakes and present a perspective on promising avenues for further studies on CrSBr.

Impact of Spin-Entropy on the Thermoelectric Properties of a 2D Magnet.

Heat-to-charge conversion efficiency of thermoelectric materials is closely linked to the entropy per charge carrier. Thus, magnetic materials are promising building blocks for highly efficient energy harvesters as their carrier entropy is boosted by a spin degree of freedom. In this work, we investigate how this spin-entropy impacts heat-to-charge conversion in the A-type antiferromagnet CrSBr. We perform simultaneous measurements of electrical conductance and thermocurrent while changing magnetic order using the temperature and magnetic field as tuning parameters. We find a strong enhancement of the thermoelectric power factor at around the Néel temperature. We further reveal that the power factor at low temperatures can be increased by up to 600% upon applying a magnetic field. Our results demonstrate that the thermoelectric properties of 2D magnets can be optimized by exploiting the sizable impact of spin-entropy and confirm thermoelectric measurements as a sensitive tool to investigate subtle magnetic phase transitions in low-dimensional magnets.

Electrochemical Doping of Two-Dimensional Superatomic Materials.

We report an electrochemical method for doping two-dimensional (2D) superatomic semiconductor Re6Se8Cl2 that significantly improves the material's electrical transport while retaining the in-plane and stacking structures. The electrochemical reduction induces the complete dissociation of chloride anions from the surface of each superatomic nanosheet. After the material is dehalogenated, we observe the electrical conductivity (σ) increases by two orders of magnitude while the 3D electron carrier density (n3D) increases by three orders of magnitude. In addition, the thermal activation energy (Ea) and electron mobility (µe) decrease. We conclude that we have achieved effective electron-doping in 2D superatomic Re6Se8Cl2, which significantly improves the electrical transport properties. Our work sets the foundation for electrochemically doping and tuning the transport properties of other 2D superatomic materials.

Photocatalytic Activation of Aryl(trifluoromethyl) Diazos to Carbenes for High-Resolution Protein Labeling with Red Light.

State-of-the-art methods in photoproximity labeling center on the targeted generation and capture of short-lived reactive intermediates to provide a snapshot of local protein environments. Diazirines are the current gold standard for high-resolution proximity labeling, generating short-lived aryl(trifluoromethyl) carbenes. Here, we present a method to access aryl(trifluoromethyl) carbenes from a stable diazo source via tissue-penetrable, deep red to near-infrared light (600-800 nm). The operative mechanism of this activation involves Dexter energy transfer from photoexcited osmium(II) photocatalysts to the diazo, thus revealing an aryl(trifluoromethyl) carbene. The labeling preferences of the diazo probe with amino acids are studied, showing high reactivity toward heteroatom-H bonds. Upon the synthesis of a biotinylated diazo probe, labeling studies are conducted on native proteins as well as proteins conjugated to the Os photocatalyst. Finally, we demonstrate that the conjugation of a protein inhibitor to the photocatalyst also enables selective protein labeling in the presence of spectator proteins and achieves specific labeling of a membrane protein on the surface of mammalian cells via a two-antibody photocatalytic system.

Electron and Spin Delocalization in [Co6 Se8 (PEt3 )6 ]0/+1 Superatoms.

Molecular clusters can function as nanoscale atoms/superatoms, assembling into superatomic solids, a new class of solid-state materials with designable properties through modifications on superatoms. To explore possibilities on diversifying building blocks, here we thoroughly studied one representative superatom, Co6 Se8 (PEt3 )6 . We probed its structural, electronic, and magnetic properties and revealed its detailed electronic structure as valence electrons delocalize over inorganic [Co6 Se8 ] core while ligands function as an insulated shell. 59 Co SSNMR measurements on the core and 31 P, 13 C on the ligands show that the neutral Co6 Se8 (PEt3 )6 is diamagnetic and symmetric, with all ligands magnetically equivalent. Quantum computations cross-validate NMR results and reveal degenerate delocalized HOMO orbitals, indicating aromaticity. Ligand substitution keeps the inorganic core nearly intact. After losing one electron, the unpaired electron in [Co6 Se8 (PEt3 )6 ]+1 is delocalized, causing paramagnetism and a delocalized electron spin. Notably, this feature of electron/spin delocalization over a large cluster is attractive for special single-electron devices.

Interplay between Local Moment and Itinerant Magnetism in the Layered Metallic Antiferromagnet TaFe1.14Te3.

Two-dimensional antiferromagnets have garnered considerable interest for the next generation of functional spintronics. However, many bulk materials from which two-dimensional antiferromagnets are isolated are limited by their air sensitivity, low ordering temperatures, and insulating transport properties. TaFe1+yTe3 aims to address these challenges with increased air stability, metallic transport, and robust antiferromagnetism. Here, we synthesize TaFe1+yTe3 (y = 0.14), identify its structural, magnetic, and electronic properties, and elucidate the relationships between them. Axial-dependent high-field magnetization measurements on TaFe1.14Te3 reveal saturation magnetic fields ranging between 27 and 30 T with saturation magnetic moments of 2.05-2.12 µB. Magnetotransport measurements confirm that TaFe1.14Te3 is metallic with strong coupling between magnetic order and electronic transport. Angle-resolved photoemission spectroscopy measurements across the magnetic transition uncover a complex interplay between itinerant electrons and local magnetic moments that drives the magnetic transition. We demonstrate the ability to isolate few-layer sheets of TaFe1.14Te3, establishing TaFe1.14Te3 as a potential platform for two-dimensional spintronics.

Functional Monolayers on a Superatomic Pegboard.

We advance the chemistry of apical chlorine substitution in the 2D superatomic semiconductor Re6Se8Cl2 to build functional and atomically precise monolayers on the surface of the 2D superatomic Re6Se8 substrate. We create a functional monolayer by installing surface (2,2'-bipyridine)-4-sulfide (Sbpy) groups that chelate to catalytically active metal complexes. Through this reaction chemistry, we can create monolayers where we can control the distribution of catalytic sites. As a demonstration, we create highly active electrocatalysts for the oxygen evolution reaction using monolayers of cobalt(acetylacetonate)2bipyridine. We can further produce a series of catalysts by incorporating organic spacers in the functional monolayers. The structure and flexibility of the surface linkers can affect the catalytic performance, possibly by tuning the coupling between the functional monolayer and the superatomic substrate. These studies establish that the Re6Se8 sheet behaves as a chemical pegboard: a surface amenable to geometrically and chemically well-defined modification to yield functional monolayers, in this case catalytically active, that are atomically precise. This is an effective method to generate diverse families of functional nanomaterials.

Coupling between magnetic order and charge transport in a two-dimensional magnetic semiconductor.

Semiconductors, featuring tunable electrical transport, and magnets, featuring tunable spin configurations, form the basis of many information technologies. A long-standing challenge has been to realize materials that integrate and connect these two distinct properties. Two-dimensional (2D) materials offer a platform to realize this concept, but known 2D magnetic semiconductors are electrically insulating in their magnetic phase. Here we demonstrate tunable electron transport within the magnetic phase of the 2D semiconductor CrSBr and reveal strong coupling between its magnetic order and charge transport. This provides an opportunity to characterize the layer-dependent magnetic order of CrSBr down to the monolayer via magnetotransport. Exploiting the sensitivity of magnetoresistance to magnetic order, we uncover a second regime characterized by coupling between charge carriers and magnetic defects. The magnetoresistance within this regime can be dynamically and reversibly tuned by varying the carrier concentration using an electrostatic gate, providing a mechanism for controlling charge transport in 2D magnets.

Anisotropic Gigahertz Antiferromagnetic Resonances of the Easy-Axis van der Waals Antiferromagnet CrSBr.

We report measurements of antiferromagnetic resonances in the van der Waals easy-axis antiferromagnet CrSBr. The interlayer exchange field and magnetocrystalline anisotropy fields are comparable to laboratory magnetic fields, allowing a rich variety of gigahertz-frequency dynamical modes to be accessed. By mapping the resonance frequencies as a function of the magnitude and angle of applied magnetic field, we identify the different regimes of antiferromagnetic dynamics. The spectra show good agreement with a Landau-Lifshitz model for two antiferromagnetically coupled sublattices, accounting for interlayer exchange and triaxial magnetic anisotropy. Fits allow us to quantify the parameters governing the magnetic dynamics: At 5 K, the interlayer exchange field is µ0HE = 0.395(2) T, and the hard and intermediate-axis anisotropy parameters are µ0Hc = 1.30(2) T and µ0Ha = 0.383(7) T. The existence of within-plane anisotropy makes it possible to control the degree of hybridization between the antiferromagnetic resonances using an in-plane magnetic field.

Increased Molecular Conductance in Oligo[n]phenylene Wires by Thermally Enhanced Dihedral Planarization.

Coherent tunneling electron transport through molecular wires has been theoretically established as a temperature-independent process. Although several experimental studies have shown counter examples, robust models to describe this temperature dependence have not been thoroughly developed. Here, we demonstrate that dynamic molecular structures lead to temperature-dependent conductance within coherent tunneling regime. Using a custom-built variable-temperature scanning tunneling microscopy break-junction instrument, we find that oligo[n]phenylenes exhibit clear temperature-dependent conductance. Our calculations reveal that thermally activated dihedral rotations allow these molecular wires to have a higher probability of being in a planar conformation. As the tunneling occurs primarily through π-orbitals, enhanced coplanarization substantially increases the time-averaged tunneling probability. These calculations are consistent with the observation that more rotational pivot points in longer molecular wires leads to larger temperature-dependence on conductance. These findings reveal that molecular conductance within coherent and off-resonant electron transport regimes can be controlled by manipulating dynamic molecular structure.

Highly Twisted Azobenzene Ligand Causes Crystals to Continuously Roll in Sunlight.

Direct conversion of solar energy to mechanical work promises higher efficiency than multistep processes, adding a key tool to the arsenal of energy solutions necessary for our global future. The ideal photomechanical material would convert sunlight into mechanical motion rapidly, without attrition, and proportionally to the stimulus. We describe crystals of a tetrahedral isocyanoazobenzene-copper complex that roll continuously when irradiated with broad spectrum white light, including sunlight. The rolling results from bending and straightening of the crystal due to blue light-driven isomerization of a highly twisted azobenzene ligand. These findings introduce geometrically constrained crystal packing as a strategy for manipulating the electronic properties of chromophores. Furthermore, the continuous, solar-driven motion of the crystals demonstrates direct conversion of solar energy to continuous physical motion using easily accessed molecular systems.

Superatom Regiochemistry Dictates the Assembly and Surface Reactivity of a Two-Dimensional Material.

The area of two-dimensional (2D) materials research would benefit greatly from the development of synthetically tunable van der Waals (vdW) materials. While the bottom-up synthesis of 2D frameworks from nanoscale building blocks holds great promise in this quest, there are many remaining hurdles, including the design of building blocks that reliably produce 2D lattices and the growth of macroscopic crystals that can be exfoliated to produce 2D materials. Here we report the regioselective synthesis of the cluster [trans-Co6Se8(CN)4(CO)2]3-/4-, a "superatomic" building block designed to polymerize and assemble into a 2D cyanometalate lattice whose surfaces are chemically addressable. The resulting vdW material, [Co(py)4]2[trans-Co6Se8(CN)4(CO)2], grows as bulk single crystals that can be mechanically exfoliated to produce flakes as thin as bilayers, with photolabile CO ligands on the exfoliated surface. As a proof of concept, we show that these surface CO ligands can be replaced by 4-isocyanoazobenzene under blue light irradiation. This work demonstrates that the bottom-up assembly of layered vdW materials from superatoms is a promising and versatile approach to create 2D materials with tunable physical and chemical properties.

Broad-band Chiral Absorbance of Visible Light.

The amplification of chiral absorbance and emission is a primary figure of merit for the design of chiral chromophores. However, for dyes to be practically relevant in chiroptical applications, they must also absorb and/or emit chiral light over broad wavelength ranges. We investigate the interplay between molecular symmetry and broad-band chiral absorbance in a series of [6]helicenes. We find that an asymmetric [6]helicene containing two distinct chromophores absorbs chiral light across a much wider wavelength range than the symmetric [6]helicenes investigated here. Chemically reducing the helicenes shifts the absorption edge of the ECD spectra into the near-infrared wavelength range while preserving broad chiral absorption, producing a [6]helicene that absorbs a single handedness of light across the entire visible wavelength range.

Controlling Ligand Coordination Spheres and Cluster Fusion in Superatoms.

We show that reaction pathways from a single superatom motif can be controlled through subtle electronic modification of the outer ligand spheres. Chevrel-type [Co6Se8L6] (L = PR3, CO) superatoms are used to form carbene-terminated clusters, the reactivity of which can be influenced through the electronic effects of the surrounding ligands. This carbene provides new routes for ligand substitution chemistry, which is used to selectively install cyanide or pyridine ligands which were previously inaccessible in these cobalt-based clusters. The surrounding ligands also impact the ability of this carbene to create larger fused clusters of the type [Co12Se16L10], providing underlying information for cluster fusion mechanisms. We use this information to develop methods of creating dimeric clusters with functionalized surface ligands with site specificity, putting new ligands in specific positions on this anisotropic core. Finally, adjusting the carbene intermediates can also be used to perturb the geometry of the [Co6Se8] core itself, as we demonstrate with a multicarbene adduct that displays a substantially anisotropic core. These additional levels of synthetic control could prove instrumental for using superatomic clusters for many applications including catalysis, electronic devices, and creating novel extended structures.

High-Spin Superatom Stabilized by Dual Subshell Filling.

Quantum confinement in small symmetric clusters leads to the bunching of electronic states into closely packed shells, enabling the classification of clusters with well-defined valences as superatoms. Like atoms, superatomic clusters with filled shells exhibit enhanced electronic stability. Here, we show that octahedral transition-metal chalcogenide clusters can achieve filled shell electronic configurations when they have 100 valence electrons in 50 orbitals or 114 valence electrons in 57 orbitals. While these stable clusters are intrinsically diamagnetic, we use our understanding of their electronic structures to theoretically predict that a cluster with 107 valence electrons would uniquely combine high stability and high-spin magnetic moment, attained by filling a majority subshell of 57 electrons and a minority subshell of 50 electrons. We experimentally demonstrate this predicted stability, high-spin magnetic moment (S = 7/2), and fully delocalized electronic structure in a new cluster, [NEt4]5[Fe6S8(CN)6]. This work presents the first computational and experimental demonstration of the importance of dual subshell filling in transition-metal chalcogenide clusters.

Site-Selective Surface Modification of 2D Superatomic Re6Se8.

Coating two-dimensional (2D) materials with molecules bearing tunable properties imparts their surfaces with functionalities for applications in sensing, nanoelectronics, nanofabrication, and electrochemistry. Here, we report a method for the site-selective surface functionalization of 2D superatomic Re6Se8Cl2 monolayers. First, we activate bulk layered Re6Se8Cl2 by intercalating lithium and then exfoliate the intercalation compound Li2Re6Se8Cl2 in N-methylformamide (NMF). Heating the resulting solution eliminates LiCl to produce monolayer Re6Se8(NMF)2-x (x ≈ 0.4) as high-quality nanosheets. The unpaired electrons on each cluster in Re6Se8(NMF)2-x enable covalent surface functionalization through radical-based chemistry. We demonstrate this to produce four previously unknown surface-functionalized 2D superatomic materials: Re6Se8I2, Re6Se8(SPh)2, Re6Se8(SPhNH2)2, and Re6Se8(SC16H33)2. Transmission electron microscopy, chemical analysis, and vibrational spectroscopy reveal that the in-plane structure of the 2D Re6Se8 material is preserved through surface functionalization. We find that the incoming groups control the density of vacancy defects and the solubility of the 2D material. This approach will find utility in installing a broad array of chemical functionalities on the surface of 2D superatomic materials as a means to systematically tune their physical properties, chemical reactivity, and solution processability.

Interlayer electronic coupling on demand in a 2D magnetic semiconductor.

When monolayers of two-dimensional (2D) materials are stacked into van der Waals structures, interlayer electronic coupling can introduce entirely new properties, as exemplified by recent discoveries of moiré bands that host highly correlated electronic states and quantum dot-like interlayer exciton lattices. Here we show the magnetic control of interlayer electronic coupling, as manifested in tunable excitonic transitions, in an A-type antiferromagnetic 2D semiconductor CrSBr. Excitonic transitions in bilayers and above can be drastically changed when the magnetic order is switched from the layered antiferromagnetic ground state to a field-induced ferromagnetic state, an effect attributed to the spin-allowed interlayer hybridization of electron and hole orbitals in the latter, as revealed by Green's function-Bethe-Salpeter equation (GW-BSE) calculations. Our work uncovers a magnetic approach to engineer electronic and excitonic effects in layered magnetic semiconductors.