Research articles

A van der Waals epitaxial strategy is reported for growing intrinsic quantum dots (QDs) by modulating interfacial couplings on van der Waals surfaces. This method overcomes lattice mismatch constraints and produces versatile III–V and IV–VI QDs with controllable morphologies, broadening near-infrared photoresponse in InSb QDs/MoS₂ by efficient interlayer charge transfer.

The fragmentation of crystallization-driven self-assembly nanomaterials is only achievable with external stimuli. Now we report that two-dimensional platelets containing less stable domains can spontaneously fragment upon ageing, providing a simple one-step method for creating hollow platelet polymer particles.

High-index facet nanostructures are deliberately targeted and synthesized by using a data-driven approach that integrates high-throughput density functional theory calculations, machine learning and experimental validation. The effectiveness of this approach is shown by the discovery and subsequent synthesis of seven monometallic and four multimetallic tetrahexahedron-shaped high-index facet nanoparticles.

The rational design and synthesis of dual-atom catalysts with structurally uniform and flexible active sites remains challenging. Now the tailored synthesis of a Janus Fe–Co dual-metal catalyst is reported in which the Fe and Co atoms are coordinated to N and O, respectively, and linked through bridging N and O atoms.

An unstrained allylic C(sp³)–C(sp³) bond is transformed into a new C(sp³)–C(sp³) bond enantioselectively with palladium catalysts via kinetic resolution or dynamic kinetic asymmetric transformation (DYKAT). Mechanistic experiments and density functional theory calculations reveal that the deracemization needed for DYKAT occurs via the formation of diene intermediates.

Automated iterative small-molecule synthesis has generally been limited to around one carbon–carbon bond-forming step per day. Now, a next-generation automated synthesizer enables rapid, automated, iterative synthesis of a variety of small molecules. Improvements to chemistry and automation leads to a tenfold decrease in reaction time over previous automated platforms.

Electrochemical methods have great potential to help achieve net-zero emissions. Here, a method to synthesize ethylene carbonate is reported, which is electrochemically initiated and enables the concurrent production of hydrogen, capture of CO₂ and subsequent conversion of the captured CO₂ during ethylene carbonate synthesis.

Exploring artificial photosynthesis with water, air and light is a challenging goal. Here, a donor–acceptor porous framework photocatalyst enables efficient production of hydrogen peroxide from aerated water under ambient conditions.

The synthesis, isolation and characterization of palladium complexes featuring one, two and three anionic aluminium ligands are reported, in which the aluminium ligands effectively stabilize the palladium in the zero-oxidation state. The aluminium–palladium bonds are highly polarized and the negatively charged palladium centre readily undergoes activation of B–B and C–N bonds.

The isolation of secondary and primary carbon radical species is challenging, owing to their instability. Now the reduction of an acyclic bis(imino)carbene conjugate acid enables the isolation of a stable pentadienyl-type radical. In silico and in vitro probing of its properties reveal a propensity to act as a secondary carbon radical.

Biocatalytic methods for the synthesis of isoindolones, via C–H activation, have remained elusive. Now, an enantiodivergent artificial-metalloenzyme-catalysed method for the synthesis of chiral isoindolones is reported, using a streptavidin–biotin–Rh(III) catalyst system. Crystallographic analysis reveals the key residues that control stereoselectivity in streptavidin.

The in situ generation of reactive (di)gallenes from a gallium–fluorobenzene complex and commercial chiral and achiral bisphosphine ligands is presented. The Ga(I) complex cations can undergo reversible cycloadditions to 1-alkenes and bond insertions into H–Si and H–B bonds.

Development of fluorine rebound processes at an enzymatic Fe(III) centre are a challenge. Now, a plant-derived non-haem iron enzyme, 1-aminocyclopropane-1-carboxylic acid oxidase, is repurposed and evolved to catalyse chemo- and enantioselective C(sp³)–H fluorination, forming a range of enantioenriched organofluorine products.

A computationally guided approach was used to predict the hierarchical assembly of four trigonal-shaped organic cage compounds into a more symmetric, higher-order, tetrahedral-shaped ‘cage of cages’ that crystallizes into a porous superstructure.

Enantioselective triple [2 + 2 + 2] cycloadditions are reported that enable the synthesis of 3D π-extended carbo[11] and [13]helicenes, which show excellent circularly polarized luminescence brightness (up to 513 M⁻¹ cm⁻¹), the highest value among helicene derivatives.

Renewable electricity-driven nitrogen oxidation is a green alternative to Haber–Bosch and Ostwald processes, but it is challenging to effectively steer oxygen intermediates towards the nitrogen oxidation reaction pathway. Now, to mitigate competing oxygen evolution and improve nitrogen oxidation efficiency, the use of hydroxyl radicals as the nitrogen oxidant is proposed.

Atomically thin gold nanosheets are predicted to have interesting properties but their synthesis is challenging. Here the exfoliation of two-dimensional single-atom-thick gold, termed goldene, is achieved through wet-chemically etching Ti₃C₂ from Ti₃AuC₂. The synthesized goldene has promising properties as a heterocatalyst.

The controlled degradation of larger and potentially harmful molecules into smaller, and preferably valuable, products is a crucial step to close the waste–degradation–synthesis loop envisioned by circular chemistry. Now, a forward-synthesis algorithm is designed to facilitate such degradation-oriented analyses, and proof-of-concept experimental validation is provided.

Palladium-catalysed C(sp³)–H amination reactions of carboxylic acids are challenging due to N-coordination often outcompeting the carboxylic acid directing effect. Now, the development of chlorinated pyridine–pyridone ligands for palladium-catalysed methylene C(sp³)–H lactamization and cycloamination is reported, enabling the synthesis of lactams and cyclic amines.

Quaternary oxides can be synthesized from a variety of precursors, but there is a poor understanding of how to design efficient synthesis recipes. Here a strategy to navigate high-dimensional phase diagrams in search of the best precursors for quaternary oxide materials is reported and validated experimentally by a robotic laboratory.