Reviews & Analysis

Charge-selective contacts have a key role in increasing the efficiency of perovskite solar cells (PSCs). A hole-transport material (HTM) is designed based on a symmetric aromatic molecule that facilitates long-range ordered π–π stacking on substrates. This HTM shows enhanced charge-transport properties, and when incorporated into PSCs, helps to deliver good efficiency and stability.

Photo-electrocatalysis under alternating polarity allows enantioselective redox-neutral cross-coupling through β-scission of alcohols to afford optically pure chiral α-arylated amines.

Thianthrene, long used in materials science, has recently emerged as a powerful reagent in organic synthesis. Its unique electronic structure enables access to diverse aryl, alkenyl and alkyl thianthrenium salts, which exhibit reactivity beyond conventional (pseudo)halides. This Review highlights the fundamental properties, distinctive reactivity and synthetic applications of these thianthrenium salts.

Selective functionalization of methylene C−H bonds at distal positions remains a challenge. Now, through ligand design, the Pd-catalysed activation of distal methylene C(sp³)–H groups in free carboxylic acids for the assembly of γ,δ-benzocyclobutene (BCB) acids is demonstrated. This approach enables the preparation of diverse BCBs from simple starting materials.

Three-component, iron-based catalytic transformations offer a promising and sustainable approach to building complex molecules in a single step. This Review highlights advances and ongoing challenges in the development of iron-catalysed difunctionalization of alkenes. Mechanistic insights that enhance our understanding and guide the development of new transformations are discussed.

Two-dimensional (2D) perovskite passivation layers can enhance the performance of perovskite solar cells but controlling their phase purity remains a challenge. Now, a non-invasive surface reaction (NSR) strategy enables the formation of phase-pure 2D perovskite passivation layers with controlled dimensions. Devices based on NSR-treated perovskites show good efficiency and operational stability.

Post-synthetic modification of olefin moieties to form coumarin linkages within covalent organic frameworks enhances their stability.

Design of anomeric leaving groups with pendant H-bond acceptors results in a stereospecific chemical O-glycosylation with broad scope and applicability to automated synthesis.

The guidance of experimental studies with computational exploration of reaction mechanisms has become a key tool in chemistry. This Perspective highlights challenges and best practices for generating reliable, reproducible and reusable data for quantum chemical calculations of reaction free-energy profiles.

Light-driven chemical reactivity enables a synthetic system to give rise to protocells with dynamic, life-like behaviour.

One-carbon compounds, including carbon dioxide and methane, represent a sustainable resource for chemical conversions. This Review highlights recent advances in the biochemical upgrading of one-carbon substrates to value-added products using a combination of cellular, cell-free and abiotic catalysis strategies.

Crystalline 2D mechanically interlocked polymers synthesized through supramolecular templating demonstrate 47-fold stiffness enhancement upon exfoliation with preserved structural order.

Asymmetric migratory cross-couplings that proceed through heteroatom-based group migration are challenging. Now, a nickel-catalysed cross-coupling reaction of amino alcohol-derived sulfonates with various carbon-based electrophiles, enabled by a radical 1,2-amino migration process, is reported. Using chiral biimidazoline ligands, diverse β-arylethylamines can be accessed with high stereoselectivity and reactivity.

Controlling the synthesis of semiconductor nanoclusters — or artificial atoms — is a challenge. Now, a programmable method is introduced to create a series of precisely defined semiconductor clusters, Zn₁₄Se₁₃, Cd₁₄Se₁₃ and Hg₁₄Se₁₃, which exhibit atom-like electronic structures and distinct doublet absorptions.

A method for the synthesis of oligosulfonimidates with control of the monomer sequence and the stereogenicity at each of the S(VI) atoms is demonstrated. This approach hinges on the use of robust and enantiospecific sulfur–fluoride and sulfur–phenolate exchange reactions and also allows for the efficient synthesis of chiral sequence-controlled polymers.

Combining cathodic oxygen reduction with anodic glycerol oxidation results in simultaneous chemical synthesis and renewable electricity production.

Stereochemical integrity is preserved in an intramolecular Friedel–Crafts alkylation, enabling the synthesis of axially chiral spirocarbons. Leveraging this stereoretentive alkylation, an iterative synthetic approach is developed for constructing enantiopure multispirocarbon-bridged carbocycles through a one-shot stereospecific conversion of chiral tertiary alcohol units, in a ‘zipping-up’ process.

The synthesis of fully π-conjugated carbon nanobelts has been a long-standing challenge. Now, through the introduction of pentagonal rings, fully π-conjugated non-alternant carbon nanobelts are realized. These nanobelts exhibit smaller band gaps and more effective π-conjugation than all-benzenoid counterparts.

Highly efficient and stable perovskite solar cells are fabricated by introducing a molecular sieve which finely controls the 2D/3D heterointerface reactions.

A catalytic asymmetric intramolecular reaction is developed for the [5+2] cycloaddition of oxidopyrylium ylides, enabled by chiral phosphoric acid organocatalysts, providing access to bridged bicyclic scaffolds.