Search

Paramagnetic heterometallic rings have long been considered as possible qubits within a quantum information processing system. Here, the authors employ supramolecular chemistry to fabricate multiple rings around multi-armed threads, as an important step towards generating useful qubit arrays.

Molecular spin qubits show great promise for quantum information processing, but loss of phase information due to noise interference hinders their applicability. Here the authors engineer the electronic configurations of the metal centres in a series of divalent rare-earth complexes and succeed in prolonging their phase memory times.

Nitrogen oxides are major air pollutants; capture and abatement technologies exist but they typically involve toxic species or precious-metal catalysts. Now, a metal–organic framework has been shown to store NO₂ dimers selectively, and to separate NO₂ from other gases under wet conditions. Treatment with water in air leads to conversion of NO₂ into HNO₃—an important feedstock for fertilizer production—with full recovery of the host.

Covalency in actinide–­ligand bonding is poorly understood compared to that in other parts of the periodic table due to the lack of experimental data. Here, pulsed electron paramagnetic resonance methods are used to directly measure the electron spin densities at coordinated ligands in molecular thorium and uranium complexes.

The ability to assemble weakly-interacting subsystems is a prerequisite for implementing quantum-information processing. In recent years, molecular nanomagnets have been proposed as suitable candidates for qubit encoding and manipulation, with antiferromagnetic Cr₇Ni rings of particular interest. It has now been shown that such rings can be chemically linked to each other and the coupling between their spins tuned through the choice of chemical linker.

Superatoms are metal clusters that collectively behave like an atom, but they usually require metal–metal bonding and thus they are based on main group or transition metals. Now it has been shown that trithorium nanoclusters with delocalized three-centre-one-electron thorium–thorium bonding exhibit exalted diamagnetism. This unveils actinide superatoms that exhibit open-shell jellium aromaticity.

The partial oxidation of CH₄ to CH₃OH is challenging to perform in artificial systems due to ready over-oxidation to CO and CO₂. Here by confining mono-iron hydroxyl sites in a metal–organic framework, photo-oxidation of CH₄ to CH₃OH is achieved with high selectivity and time yield.

The construction of C-C bonds via reductive coupling carbonyl compounds is a huge challenge in organic transformations. Here, the authors develop a highly efficient system for the photoreductive coupling of aldehydes and ketones to the corresponding 1,2-diols under mild conditions.

Gaining molecular-level insight into host–guest binding interactions is fundamentally important, but experimentally challenging. Here, Schröder and co-workers study CO₂–host hydrogen bonding interactions in a pair of isostructural redox-active V^III/V^IVMOFs using neutron scattering and diffraction techniques.

Ligand design contributes to dictating the magnetic properties of lanthanide-based single-molecule magnets. Here, the authors report a series of phosphorus-ligated dysprosium complexes, and show that the dynamic magnetic properties change as the ligand is varied from phosphine to phosphide to phosphinidene.

Lower olefins are mainly produced from fossil resources and the methanol-to-olefins process offers a new sustainable pathway. Here, the authors show a new zeolite containing tantalum and aluminium centres which shows simultaneously high propene selectivity, catalytic activity, and stability for the synthesis of propene.

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

Electrochemical reduction of carbon dioxide is a highly attractive strategy for the production of organic products of economic value. Here, the authors report the electrochemical reduction of carbon dioxide to formic acid over a copper-based metal–organic framework decorated electrode at low over-potential.

Production of olefins from biomass-derived γ-valerolactone could lead to sustainable chemical processes, but catalysts suffer from deactivation due to water. Here, a MFI-type zeolite doped with Nb(v) and Al(iii) shows >99% yield at 320 °C and catalyst stability over 180 hours.

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.

In coordination and organometallic chemistry, back-bonding between an electron-rich, typically mid- or low-oxidation-state d-block metal centre and a ligand with accepting π* orbitals is widespread. Now, such an interaction has been observed between unlikely partners—high-oxidation-state uranium(v) 5f¹ ion and the poor π-acceptor ligand dinitrogen—in a U(v)–bis(imido)–N₂ complex stabilized by a lithium counterion.

Mechanically interlocked molecules and molecular cages are two important themes in supramolecular chemistry. Here, the authors combine these concepts to construct a giant [13]rotaxane built around a palladium capsule, one of the most complex metallosupramolecular assemblies yet.

The nature of actinide–ligand bonding is attracting attention, in particular in the context of nuclear waste separations. Structurally authenticated one-, two- and threefold uranium–arsenic bonding interactions are now reported. Computational analysis suggests the presence of polarized σ², σ²π², and σ²π⁴ in the arsenide, terminal arsinidene, and arsenido complexes, respectively.

Actinide electronic structure determination is fundamentally challenging. Here, the authors assemble a family of uranium(V)-nitrides and quantify the electronic structure of the molecules, defining the relative importance of spin orbit coupling and crystal field interactions.

The physical implementation of quantum information processing requires individual qubits and entangling gates. Here, the authors demonstrate a modular implementation through chemistry, assembling molecular {Cr₇Ni} rings acting as qubits, with supramolecular structures realizing gates by choice of the linker.

Dysprosium alkoxides and dysprosium-doped yttrium alkoxides show very large energy barriers, greater than 800 K, to magnetic relaxation. These barriers arise from the presence of a strongly axial pseudo-octahedral crystal field, which switches off relaxation through the first excited state that typically occurs in single-molecule magnets, and favours a competitive pathway through higher-energy states.

A terminal uranium(VI)–nitride has been shown to be accessible and isolable by a redox strategy whereas a photochemical approach resulted in decomposition. Computational analyses suggest that the U≡N triple bonds are surprisingly comparable to analogous group 6 transition metal nitrides, with a covalent character dominated by 5f rather than 6d contributions.

The inverse-trans-influence has been shown to operate in high oxidation state actinide complexes. Here, the authors report tetravalent cerium, uranium and thorium bis(carbene) complexes with trans C=M=C cores where experimental and theoretical data also suggest the presence of an inverse-trans-effect.

Owing to the propensity for uranium(III) compounds to undergo disproportionation, uranium-element multiple bonds involving uranium(III) oxidation states remain rare. Here the authors report hexauranium-methanediide rings that formally contain uranium(III)- and uranium(IV)-methanediides supported by alternating halide and arene bridges.

The reactivity of f-block complexes is primarily defined by single-electron oxidations and σ-bond metathesis. Here, Liddle and co-workers provide evidence that a uranium complex can undergo reversible oxidative addition and reductive elimination, demonstrating transition metal-like reactivity within f-block chemistry.

Lytic polysaccharide monooxygenases (LPMOs) are a class of copper-dependent enzymes that oxidatively degrade polysaccharides and find use in industrial processing of lignocellulose. Crystallographic and spectroscopic studies define how LPMOs recognize their oligosaccharide substrates and mediate oxidative cleavage.

High and reversible nitrogen dioxide (NO₂) uptake, and low-concentration NO₂ removal from gas mixtures, is observed in a metal–organic framework. The NO₂ is bound within the pores by cooperative supramolecular interactions.

Producing ammonia is challenging and requires efficient and selective catalysts to drive the reaction. Here, a series of single-atom catalysts derived from UiO-66 containing structural defects show efficient electrochemical reduction of nitrate to ammonia.