f-block elements

Molecular nanomagnets exhibit magnetic memory effect originating from each individual molecule. Here, the authors report an intermetallic nanomagnet based on a single Er^III center coordinated solely by three transition metals in a trigonal planar fashion.

The reasons for which many low-coordinate complexes exhibit bent geometry, rather than a higher symmetry, are still under debate. Here, the authors use high-pressure crystallography to examine whether low-coordinate f-block molecules become more planar or pyramidal under pressure; which happens is dictated by the dipole moment of the complex and the volume of the planar form.

The coordination environment has a great impact on the electronic structure, bonding and properties of metal complexes. Here the authors report a dinuclear organometallic americium complex that displays unexpectedly ionic Am−N bonding, but enhanced covalency in the Am−C bonds compared to its neodymium analogue.

The most common oxidation state for lanthanides is +3. Here the authors use photoelectron spectroscopy and theoretical calculations to study half-sandwich complexes where a lanthanide center in the oxidation state +1 is bound to an aromatic wheel-like B₈^2- ligand.

Ce(IV) organometallic compounds are rare due to Ce(IV) being a powerful oxidant. Herein, the authors explore the covalency of a pair of organocerium complexes bearing a Ce(IV)-C(aryl) bond and examine their structure by NMR spectroscopy, X-ray diffraction analysis, and computational calculations.

The obtention and study of actinide elements is challenging due to various factors including their radioactivity and scarcity. Herein, the authors characterize the atomic and electronic structure of Am, Cm, Bk, and Cf compounds using a transmission electron microscopy-based workflow that only requires nanogram amounts of the actinide element.

Disproportion of uranium(IV) is rare, as it is usually the stable product of uranium(III) or (V) disproportionation. Here, the authors report uranium(IV) disproportionation to uranium(III) and (V) revealing ligand and solvent control over a key thermodynamic property of uranium

Studying how the ligand design influences the bonding of f-block complexes is crucial to control their properties. Here, the authors report the preparation of Bk(III) and Ce(III) complexes featuring a terpyridyl ligand; structural, spectroscopic, electrochemical, and theoretical analysis reveal that the ligand induces unusual bonding by creating a plane of enhanced bond covalency.

Determining the covalency of actinide chemical bonding is a fundamentally important challenge. Here, the authors report a ¹⁵N nuclear magnetic resonance spectroscopy study of a terminal uranium-nitride, revealing exceptional NMR properties and covalency that redefine ¹⁵N NMR parameter space and actinide chemical bonding.

Metal-ligand δ and φ interactions, though considered weak, may be necessary for fully describing the electronic and geometric structures of certain compounds. Here, in actinide metallacycles, the authors discover two new types of M-L δ and φ back-bonds that contribute substantially to their unusual chemical behavior.

Lanthanide sandwich complexes represent both a fundamental class of organometallic compounds and promising molecular magnets for information storage. Here the authors unveil a class of lanthanide sandwich complexes containing fully π-coordinated 8- and 9-membered rings, and show their slow relaxation of the magnetization.

The synthesis and isolation of uranium(VI) nitride complexes remains challenging. Here, the authors report an example of transition metal (TM) stabilized U(VI) nitride complexes, generated via photolysis of azide-bridged U(IV)-TM precursors.

Developing efficient and stable earth-abundant electrocatalysts for acidic oxygen evolution reaction is challenging. Here, the authors modify the local bonding environment of Co₃O₄ by CeO2 nanocrystallites to regulate the redox properties, thus enhance the catalytic activity.

Despite their importance as mechanistic models for Haber Bosch ammonia synthesis from N₂ and H₂, high oxidation state terminal metal-nitrides are notoriously unreactive towards H₂. Here, the authors report hydrogenolysis of a uranium(V)-nitride, which can occur directly or by Frustrated Lewis Pair chemistry with a borane ancillary.

Renewable hydrogen technologies are promising for alternative energy, but are encumbered by the kinetics of electrochemical reactions in harsh conditions. Here, authors report nitrogen-modified hafnium oxyhydroxide for electrocatalysis of hydrogen evolution and oxidation reactions in acidic media.

Electrodeposition provides a facile fabrication means for electrochemical devices but weak substrate-deposit interactions cause poor performance. Here, authors utilize anion insertion within graphitic layers to improve the material interfaces and construct highly active O₂-evolving electrocatalysts.

Solar-to-chemical CO₂ reduction provides a means to use light’s energy for CO₂ removal and upgrading to useful products, although this photochemical conversion is challenging. Here, authors construct a Europium-containing metal-organic framework that selectively converts CO₂ to formate with light.

There is an increasing interest in understanding how defect chemistry can alter material reactivity. Here, authors tune the electronic structure of RuO₂ by introducing W and Er dopants that boost acidic oxygen evolution performances by limiting oxygen vacancy formation during catalysis.

While renewable H₂ evolution will require inexpensive, abundant catalysts, non-noble metals typically show relatively low activities. Here, authors examine lanthanide metal sesquioxide doped metallic Ni and show efficient, stable performances for alkaline H₂ evolution electrocatalysis.

The preparation of lanthanide-transition metal clusters containing multiple lanthanide atoms remains challenging. Here, the authors present the controlled on-surface formation of ligand-stabilized heterometallic Ce/Au clusters containing two, three and four Ce atoms bridged by Au adatoms.

Great progress has been made in topochemistry of mobile oxygen anions, but metastable compounds have not yet been achieved by deintercalation of sulfur anions. Here, the authors prepare metastable oxychalcogenide phases by taking advantage of redox-reactive sulfur dimers embedded in a layered oxysulfide.

Lanthanoid complexes are widely used for various applications but so far it is difficult to combine multiple lanthanoids into one single molecular entity with sufficient stability. Here, the authors report a method for this purpose using peptide synthesis, and show that a trinuclear lanthanoid complex can be used to create a luminescence nanocode.

Radiation dosimeters that measure ionizing radiations over a broad range and allow for direct readout are desirable. Here, the authors present a dual-mode photochromic thorium-based metal-organic nanocluster that enables direct visible colorimetric dosimetry of UV, β-ray, and γ-ray radiation.

Compounds featuring long-lived luminescence have potential applications in a variety of fields, including anti-counterfeiting and switches. Here the authors report a lanthanide-based compound that exhibits phosphorescence observable by the naked eye for up to 30 s at 77 K; On-off continuous irradiation cycles reveal a charging behaviour associated with triplet-triplet absorption, showing a shorter rise lifetime than the decay lifetime.

Host-guest supramolecular chemistry can be used as a tool to develop multicolor displays. Here, the authors present a system based on lanthanide-cradled cyclodextrins that allows to construct MRI-readable and erasable artificial non-luminescent color palettes.

Precisely controlling the chemical composition and structure of nanoclusters is an ongoing challenge. Here, the authors report a clickable assembly strategy to construct widely varied lanthanide nanoclusters with synergized optical functionalities.

Though divalent-europium-based complexes are promising materials for next-generation light-emitting devices, their poor air stability limits their applicability. Here, the authors report the design of air stable divalent-europium-based complexes for efficient organic light-emitting diodes.

Materials with oxygen hyperstoichiometry received great attention in solid oxide fuel cells field because of the low activation energy of interstitial ion migration. Here the authors revealed the relationship between the structure and oxide ion migration for the whole series of CeNbO4+δ compounds.

Radionuclides are of great importance for fields such as nuclear medicine and waste recycling, but their efficient purification remains a challenge. Here the authors show that an octadentate hydroxypyridinone chelator enables efficient and robust separation processes for isotopes of Ac, Pu, and Bk.

The separation of the rare-earth elements is a significant scientific challenge. Here, the authors report the selective precipitation of the light rare-earths as supramolecular capsules from acidic, industrially relevant, mixed-metal solutions.

Lanthanide ions possess similar chemical properties, making their separation from one another challenging. Here the authors show that a tris-tridentate ligand causes high-precision metal ion self-sorting, leading to the selective assembly of tetrahedral M₄L₄ cages across the lanthanide series.

For molecular magnets and qubits, coupling between vibrations and electronic spins has a strong influence on spin state lifetime. Here, Kragskow et al present direct measurements of the vibronic transitions in a molecular magnet, showing the critical role of an “envelope effect” in the spectra.

The nature of quantum criticality in intermetallic f-electron compounds exhibiting valence fluctuations is not well understood. Here, using a combination of experimental techniques, the authors attribute quantum criticality in YbAlB₄ to the anisotropic hybridization between the conduction and f-electrons.

Negative pressure tailors the physical properties of functional oxide materials. Here, the authors demonstrate an emergent multiferroism with magnetodielectric coupling in EuTiO₃ created by a negative pressure control of strong spin-phonon coupling.

Charge-neutral excitations have been proposed to explain metal-like thermal transport in Kondo insulators. Here, the authors demonstrate the coupling between charge-neutral excitations and spin degrees of freedom in a Kondo insulator YbIr₃Si₇, which puts restrictions on current theories.

Magnetic topological materials have a variety of interesting properties, but very few material realizations exist. Here, the authors report a topological nodal-line semimetal and a topological massive Dirac metal phase in EuAs₃ and demonstrate a magnetism-driven transition between these phases.

Merons and Skyrmions, two topological spin-textures, have attracted a lot of interests due to their potential use in information storage. Here, the authors demonstrate the transformation of Meron pairs into Skyrmions without an applied magnetic field within domain walls of GdFeCo films.

It remains an open question as to whether the quantum spin liquid state survives material disorder, or is replaced by some spin-liquid like state. Here, Rao et al succeed in resolving a resolving a κ₀/T residual in the thermal conductivity of YbMgGaO₄ strongly suggesting the survival of the quantum spin liquid state.

The mechanism of the delocalization transition of 4f electrons in closely-packed Ce metal has been debated. Here, the authors present photoemission evidence for bandwidth-controlled Mott delocalization in a previously unreported structural phase of thin epitaxial Ce films obtained by thermal annealing.

The spin exchange, which is central to spintronics, has been restricted to devices with long-range magnetic ordering to date. Here, Pei et al. design a single-molecule-magnet and utilize its internal spin exchange to control the current through a single-molecule junction with high spin polarization (>95%).