Browse Articles

Electrochemical isotope separation offers an alternative to conventional energy-intensive separation processes, but the mechanism underpinning ¹³C enrichment is unclear. Now, a relationship is established between catalyst design and isotopologue enrichment in CO₂ electrolysis, in a step towards a predictive and scalable strategy for carbon-isotope separation.

Manipulating and stabilizing correlated quantum states in 1T-TaS₂ remain key challenges. Now it has been shown that the commensurate charge density wave stability temperature can be elevated to 330 K via arginine intercalation, establishing a chemically tunable hybrid-superlattice strategy for tailoring correlated states and electronic orders in van der Waals materials.

Deep electrochemical reduction offers a safe and sustainable route to reduction potentials beyond the reach of many conventional reagents. In this Review, the authors detail how these conditions can enable new reactivity and transformations, and strategies to mitigate the challenges of extreme reducing environments.

Phenylalanine has a hydrocarbon side chain that is difficult to chemically modulate. Now, a bioorthogonal strategy is developed in which this side chain is caged with iodine and selectively decaged by a palladium species. This approach enables on-demand control of hydrophobic and π interactions in cells and at the cell surface.

Access to long-lived light-induced states in earth-abundant transition-metal chromophores is desirable but hard to achieve. Now, enhanced metal–ligand covalency has been shown to increase the lifetime of the photomagnetic high-spin state in a manganese photoswitch.

Electrochemical isotope separation offers continuous and mild ¹³C enrichment but the role of catalysts in the chemical mechanism remains elusive. Now, it has been shown that catalyst-directed vibrational-frequency disparities can impact isotope enrichment capabilities, establishing a predictive design principle for scalable enrichment that achieves 14% ¹³CO₂ output from natural-abundance CO₂.

Simultaneously controlling the topology and bimetallic node arrangement in conductive two-dimensional conjugated metal–organic frameworks obtained from a single ligand is challenging. Now a strategy based on a low-symmetry ligand enables site-selective and sequential coordination, yielding seven single-crystalline frameworks with distinct architectures and charge transport properties.

N-Alkyl aziridines have long resisted catalytic ring opening and existing strategies rely on electron-withdrawing N-activating groups. Now, simple borane coordination is shown to direct radical fragmentation of these substrates, providing a general platform for divergent ring-opening functionalization that streamlines access to β-functionalized amines.

Accessing metastable boron allotropes beyond those attainable through conventional thermodynamic routes is a central challenge in boron chemistry. Now, an allotrope featuring an open-framework architecture comprising B₁₂ icosahedra interconnected by triangular B₃ units has been synthesized through high-pressure formation of a Na₄B₆₀ precursor followed by sodium degassing. This allotrope exhibits both high electrical conductivity and plastic deformability.

Aziridine ring opening is a powerful strategy for molecular diversification, but direct functionalization of unactivated N-alkyl aziridines has remained a long-standing challenge. Now it has been shown that aziridine-ligated boryl radicals enable direct ring opening and divergent functionalization of N-alkyl aziridines, providing streamlined access to diverse β-functionalized amines.

Charged point defects cause efficiency loss and instability in perovskite solar cells. Although Lewis acids and bases individually passivate oppositely charged defects, they typically react with one another. Now bulky phosphine bases and fluorinated aromatic acids have been shown to enable concurrent defect passivation and power conversion efficiencies up to 27.4%.

In recent years, there has been a surge in the development of reactions using photoredox catalysis. However, the ability to reproduce these reactions varies wildly, owing to key factors such as light source, temperature control and the use of co-catalysts not being clearly defined and reported.

The de novo assembly of stereochemically complex carbohydrate mimics usually relies on traditional, protecting-group-intensive multistep synthesis. Now, it has been shown that a rhodium-catalysed triple-carbonylation cascade delivers functionalized, oxygen-rich scaffolds in a single step directly from simple aldehydes and carbon monoxide, achieving rapid complexity from readily available feedstocks.

Nitrate is a notoriously difficult substrate for molecular catalysts because of its weak metal-binding affinity and strong N–O bonds. Now, a network of secondary-sphere hydrogen-bonding interactions within an iron coordination complex has been shown to enhance nitrate binding and activation, promoting its catalytic reduction to nitric oxide and ammonia.

Peptides can assemble into two-dimensional ultrathin materials with programmable structures and functions, but maintaining crystallinity and stability is challenging. Now, a metal-directed assembly strategy enables mechanical weaving of peptides to provide highly durable and modular two-dimensional peptide crystals with molecular-level precision.

Small-molecule walkers that combine autonomy with kinetic asymmetry have remained elusive. Now, simple phosphoric acid esters are shown to drive a non-enzymatic reaction cycle that autonomously migrates a phosphate group along five hydroxy footholds, expanding the scope of synthetic molecular machinery.

Nitrogen fixation is a challenging, energy-intensive process. Now, iron salts and a molybdenum catalyst have been shown to drive the photosynthetic reduction of atmospheric nitrogen to ammonia using water as the terminal electron donor, suggesting a promising new pathway for one of the most important chemical reactions.

The charge state of oxygen vacancies, manifested as distinct F centres, remains an underexplored descriptor for electrocatalytic pathway modulation. Now it has been shown that different F centres in ZrO₂ regulate oxygen reduction via unique electronic behaviours, establishing F-centre identity as a key indicator for electrocatalytic selectivity.

Visualizing plasmon-enhanced H₂ activation and propagation on catalytic surfaces remains challenging because conventional spectroscopies lack nanoscale resolution. Now it has been shown that tip-enhanced Raman spectroscopy maps H₂ activation within an Ag tip–Pt(111) nanocavity and reveals H atoms propagating hundreds of nanometres across Pt(111) through a collective crowd effect.

Rigid coordination bonds readily generate highly connected secondary building units in metal–organic frameworks, but weaker and less directional interactions have rarely afforded comparable architectures in molecular crystals. Now ammonium halide ion pairs are shown to aggregate into discrete clusters that function as soft secondary building units, opening a route to non-metallic organic frameworks with diverse topologies.