A general and scalable approach to prepare functionalized bicyclo[1.1.1]pentanes is reported. The key reaction between alkyl iodides and propellane is performed in flow and requires just light; no catalysts, initiators or additives are needed. Combined with the subsequent functionalization, >300 bicyclo[1.1.1]pentanes for medicinal chemistry have been prepared.

Dynamic supramolecular systems can be designed to adapt phases in a pre-programmable way. Here the transient nature of a gel system is exploited, in combination with the application of mechanical stimuli, to obtain soft materials with aligned fibres in a controllable way.

Synthesis of metastable materials away from thermodynamic equilibrium has been a challenge in materials chemistry, but thin-film methods often struggle to yield ground-state structures. Now, a synthesis pathway to thin films of stable layered ternary nitrides is revealed, and the tendency for metastable intermediate formation is discussed.

Suzuki–Miyaura cross-coupling between (hetero)aryl (pseudo)halides and base-sensitive and Lewis-basic (hetero)arylboronic acids is challenging, owing to potential side reactions and catalyst poisoning. Now, the Suzuki–Miyaura cross-coupling of arylthianthrenium salts with (hetero)arylboronic acids, under acidic conditions, is reported, enabling the efficient coupling of base-sensitive and Lewis-basic (hetero)arylboronic acids.

Covalent organic frameworks (COFs) are promising photocatalysts for the direct photosynthesis of H₂O₂, but their symmetric structure can lead to weak O₂ adsorption. Now thiophene sulfur atoms are introduced into COFs to induce local asymmetric electron distributions, which enhance the O₂ adsorption capacity and interaction of the COFs, promoting direct photosynthesis of H₂O₂.

A singly bonded gallanediyl undergoes carbometalation reactions with alkynes by retaining the low +I oxidation state and the singly bonded nature of gallium. The insertion into the gallium(I)–carbon bond proceeds regioselectively and gives exclusively the syn-addition products.

An interfacially coupled Cu-cluster/GaN photocathode is designed to overcome the efficiency and stability bottlenecks in photoelectrochemical CO₂ reduction to multicarbon products. The self-optimized Ga–N–O interface facilitates and stabilizes interfacially oxidized copper species of copper clusters, which function as efficient C–C coupling sites for ethylene production.

Computational analysis of competing sulfur(VI)–fluoride exchange and modular diazotransfer pathways in the reaction between primary amines and fluorosulfuryl azide reveals that diazotransfer is more kinetically and thermodynamically favoured. Predictive models are formulated by combining mechanistic analysis and structure–activity relationship studies, enabling the development of an easy-to-prepare and highly reactive diazotransfer reagent.

Dynamic supramolecular systems can be designed to adapt phases in a pre-programmable way. Here the transient nature of a gel system is exploited, in combination with the application of mechanical stimuli, to obtain soft materials with aligned fibres in a controllable way.

Synthesis of metastable materials away from thermodynamic equilibrium has been a challenge in materials chemistry, but thin-film methods often struggle to yield ground-state structures. Now, a synthesis pathway to thin films of stable layered ternary nitrides is revealed, and the tendency for metastable intermediate formation is discussed.

Electrocatalytic synthesis of chemicals and fuels is seen as one way to decarbonize the chemicals industry. In this focus issue, we examine the electrochemical coupling of CO₂ with heteroatoms for sustainable chemical synthesis.