Articles

Although transition metal-based complexes featuring metal atoms in formally negative oxidation states are known, their stabilization without an organic ligand remains challenging. Now, lanthanide–nickel intermetallic complexes featuring an organic-ligand-free Ni²⁻ ion bound to electropositive lanthanides have been stabilized in fullerenes.

Boron-containing four-membered rings are less studied than five- and six-membered boron rings owing to limited preparative approaches. Now a triplet energy transfer strategy has been developed for the synthesis of strained, air-stable benzoboretenes through the intramolecular coupling of boron–carbon-centred diradicals. The preparation of dihydroborinine and dihydrocyclopropaborole derivatives has also been achieved.

Computational and spectroscopic studies of molecular lanthanide complexes have implicated 4f orbitals in metal–ligand bonding interactions. Now, a comparative study of isostructural d-block, actinide and lanthanide complexes has shown that 4f-orbital covalency enables ring-opening isomerization in a Ce(IV)–cyclopropenyl complex in the solid state, a reaction not observed for the other complexes studied.

The hetero-Diels–Alder reaction is a powerful strategy for constructing six-membered heterocycles, yet natural enzymatic hetero-Diels–Alder reactions are limited to a single heteroatom. Now a bifunctional enzyme, Abx₍₋₎F, is found to catalyse the dehydration and a dual-oxa Diels–Alder reaction to form the oxygen-bridged tricyclic acetal of (−)-anthrabenzoxocinones.

Nucleobase deamination can be used to map N⁶-methyladenosine in RNA, but existing deamination methods are harsh, limiting applications. Now a method for the N-nitrosation of RNA based on organocatalyst and Lewis acid co-catalysis has been shown to enable sensitive N⁶-methyladenosine mapping with minimal background noise and high detection efficiency.

The reaction between Criegee intermediates and water vapour greatly impacts atmospheric chemistry and climate, yet its dynamics remain poorly understood. Now it has been shown that syn-CH₃CHOO reacts with water vapour at rates much higher than previously estimated, through a roaming mechanism that enhances reactivity and challenges conventional understanding of atmospheric OH radical production.

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.

Membranization of membraneless coacervates and condensates offers a solution to their inherent instability, but current strategies are system specific. Now, it has been shown that condensate-amphiphilic block polymers provide robust and versatile membranization for a wide range of coacervates and condensates, substantially enhancing their mechanical stability and tolerance to extreme conditions.

Switchable skeletal editing is valuable in drug discovery, but controllable methods for chemodivergent modifications of azaarenes are challenging. Now transformations of quinolines have been achieved by leveraging cyclizative rearrangement strategies, enabling the construction of four different frameworks, including the enantioselective skeletal editing of quinolines into benzazepines.

Observing spin-changing atom–molecule collisions with quantum-state precision provides clues of short-range interactions. Now it is shown that the outcomes of the KRb + Rb collision only align with a statistical model after assuming the non-conservation of mechanical angular momentum. The observations also contradict coupled-channel calculations that neglect vibrations and conical intersections.

The most common oxidation state for lanthanide elements is +3, and, beyond cerium, examples of these elements exhibiting higher oxidation states remain scarce. Now, a molecular complex of praseodymium in the +5 oxidation state has been synthesized; this compound exhibits a unique electronic structure driven by N 2p and Pr 4f orbital contributions.

Gut microbiota play a critical role in drug metabolism. Now, by exploring the human gut microbial metabolism of G-protein-coupled receptor (GPCR)-targeting drugs, uncommon pathways and biotransformations are elucidated, revealing how the activity of the metabolized drugs against target GPCRs is modulated.

Dynamic gene expression is crucial for coordinating diverse cellular activities, but challenging to modulate with high spatiotemporal precision. Now, a photoswitchable DNA structure-specific, small-molecule ligand enables reversible, light-controlled regulation of gene expression and cell proliferation in live cells.

Transition metal oxides serve as important electrocatalysts for the oxygen evolution reaction, although Co-based oxides typically undergo pH-dependent dynamic surface reconstruction under catalytic conditions. Now the correlations between Co redox dynamics, flat band potential and Co oxidation state changes have been established to explain the pH dependency of oxygen evolution activity.

The mutual neutralization of hydronium and hydroxide ions is a reaction of fundamental interest that has recently been implicated in the generation of high concentrations of hydroxyl radicals at the surface of water microdroplets. Using three-dimensional imaging of the coincident neutral products of the reaction of D₃O⁺ and OD⁻, two competing pathways for OH radical formation have now been experimentally observed.

Although dry reforming of methane can convert CO₂ to valuable chemicals, the reaction requires near-equivalent amounts of CH₄. Now it has been demonstrated that an electro-thermocatalytic CH₄ reforming process, when combined with the reverse water–gas shift and H₂O electrolysis reactions, can efficiently catalyse CO₂-rich natural gas into syngas.

Propane dehydrogenation is challenging to perform under mild conditions due to the reaction’s endothermic nature. Now, near-ambient propane dehydrogenation has been shown using copper single-atom catalysts supported on titanium oxide under light illumination and a water vapour environment.

Chemical energy conversion and storage rely on the selective movement of protons and electrons, thus understanding these processes is important for applications. Now experiments at elevated pressures are shown to identify excited-state proton-coupled electron transfer mechanisms and to facilitate merging proton transfer with subsequent electron transfer steps towards a concerted pathway.

Achieving stereochemical control in S_N1-type nucleophilic substitution reactions is challenging due to the complexity of the successive carbocation intermediates. Now a strategy using neighbouring group participation to form cyclopropylcarbinyl cations enables the preparation of complex molecular skeletons via stereospecific S_N1 at a quaternary stereocentre in acyclic systems.

In reticular chemistry, the formation of strong chemical bonds between molecular components is typically considered a core prerequisite for synthesizing open-framework materials. Now a series of robust frameworks have been assembled through van der Waals interactions; the stacking of polyhedral molecular building blocks results in the formation of three-dimensional open diamond networks.