Themed collection 2023 ChemSci Pick of the Week Collection

We summarize the challenges to design and synthesize self-assembled molecules, discussing their synthetic routes and structural features in relationship to the efficiency of perovskite-based solar cells where they are applied as selective contacts.

We provide an overview of coordination cage catalysis, highlighting how mechanistic understanding can help address the challenges in this area leading to new opportunities in non-covalent reactivity.

This perspective highlights recent advances and challenges in transition-metal (oxy)nitrides, which are promising photocatalysts for overall water splitting, and discusses opportunities to upgrade the solar-to-hydrogen energy conversion efficiency.

Targeted protein degradation strategies employing proteins as binders for degradation targets.

The activity of Ni–Mo catalysts for the hydrogen evolution reaction originates from the interfaces of alloy–oxide or alloy–hydroxide, in which the oxide or hydroxide promotes water dissociation and the alloy accelerates hydrogen combination.

Synchrotron radiation enables probing a wide range of length scales operando, hence being a powerful tool in battery research. Challenges ahead involve cell design (especially for multi-modal approaches) and protocols for automated data analysis.

By taking inspiration from the structures and reactivities of its past, organolanthanide chemistry has managed to reinvent itself for the challenges of today and the future.

Organo-functionalisation of polyoxometalates with peptide moieties is an effective approach to obtain diverse arrays of functional hybrid materials, where each component influences the resulting change, surface chemistry, polarity, and redox properties.

This review explores the benefits of flow chemistry and dispels the notion that it is a mysterious “black box”, demonstrating how it can push the boundaries of organic synthesis through the understanding of its governing principles.

¹⁹F NMR analysis of ion-pairing and reaction kinetics shows that TBAT can act as a genuine surrogate for TBAF, as well as a reservoir for rapidly-reversible release of traces of it, to effect both direct (k_d) and dissociative (k_F) fluoride transfer.

Non-linear threshold analysis enabled discovery of a highly soluble (1.3 M) bipyrimidine anolyte. Stable cycling in a full flow battery cell for 75 cycles.

We report the discovery of an ortho regioselective oxidative halodeboronation of N-aryl amides and ureas with wide-ranging applications in pharmaceuticals, materials science, and synthetic organic chemistry.

Small molecule degraders and stabilizers of squalene synthase based on the same scaffold are reported, which respectively accelerate or block its natural degradation.

Minimal models of cages are used to map the accessible cage topologies based on building block properties.

Visible-light-absorbing photoswitches based on the Azo-BF₂ scaffold show reversible isomerization in the solid state, storing photon energy and releasing thermal energy on demand.

The electrochemical intercalation of Rb into graphite and low-crystalline carbons was demonstrated. It was confirmed that stage-1 RbC₈ was formed in the low-potential region close to the Rb plating potential (Rb⁺/Rb) in non-aqueous electrolytes.

A facile catalyst-free click polymerization of aldehyde-activated internal diynes and dithiols was established, affording multifunctional polysulfides and derivant with unique acid–base response for promising applications in diverse areas.

Aromatic acyl O-hydroxylamines, synthesised in one straightforward step, undergo rearrangement under simple conditions to give ortho-aminated arenes. For benzoic acid-derived substrates, this leads directly to unprotected anthranilic acids.

Polycatechol nanohoop ligands are readily synthesized from fluorinated precursors and metalated, opening the door to new carbon nanohoop-based metal–organic materials.

Different excited state equilibration pathways yield ground-state electron spin polarization of radical-elaborated platinum(II) complexes. The equilibration pathways are controlled through designed molecular conformation.

Rational structure–mechanism-based strategies for identifying small molecules that are able to control multiple pathological targets in Alzheimer's disease are established, with an example of developing a promising multi-target-directed flavonoid.

The synthesis of monomeric 2,3,4,5-tetraalkyl-substituted boroles via metallacycle transfer from an alumole is reported.

This paper describes a multi-tribe hybrid evolutionary algorithm that combines differential evolution and genetic algorithms for surface structural optimization accelerated by an on-the-fly machine learning calculator.

Spectroscopy and kinetics are used to evaluate the role of the secondary coordination sphere in substrate/product binding as well as reactivity in the nitrification enzyme cytochrome P460.

Human-in-the-loop experimentation enables interactive machine learning for continuous flow chemistry reaction planning and optimization.

Influence of the protonation state of the guanidinium group, present in the 2nd sphere of an iron porphyrin complex, in the reduction of nitrite to nitric oxide via {FeNO}⁶ intermediate.

Thiophene substitution at the 3-position of PQ enhances its reactivity in PQ-ERA photoclick reactions, resulting in increased efficiency, yields, rate constants, and oxygen tolerance, offering prospects for efficient photoclick transformations.

The methane pyrolysis reaction network is constructed from first principles in the ab initio nanoreactor, going from reaction discovery through ab initio molecular dynamics to chemical kinetic modeling and comparison to experiments.

We demonstrate a simple strategy to use a metal surface to directly catalyse mechanochemical reactions by Resonant Acoustic Mixing (RAM), a scalable mechanochemical methodology that uniquely eliminates the need for grinding media or bulk solvent.

The exploitation of an intermolecular Si–F interaction between the substrates, together with chiral Lewis-base catalysis, allows the regio-, diastereo- and enantioselective allylation of ketone-derived silyl enol ethers with allyl fluorides.

Mechanistic studies on sodium-mediated borylation of arenes, uncover a unique polybasic behaviour for the formal borylation of two equivalents of the relevant arene as well as the competing formation of a borata-alkene complexes.

Measurements using chemical double mutant cycles show that electron-withdrawing groups lead to remarkable increases in the stability of aromatic interactions, and the magnitude of the effect is much larger in water than in chloroform solution.

Addition of water to a 3c–2e boron gallium hydrido compound results in capturing of the parent oxoborane moiety, B(H)O. The latter reacts with another molecule of water to give a boracarboxylic acid derivative.

Ultra-stable CsMnX₃ nanocrystals embedded glasses with bright and broad red photoluminescence (PL) emission at 649 nm were synthesized as an excellent red phosphor for white light-emitting diode (LED) devices with a high color rendering index (CRI).

We report the first molecular probe for the selective detection of the most abundant cellular inositol pyrophosphate 5-PP-InsP₅, supported by computational chemistry, as well as an efficient new synthesis.

A halogen bonding anion relay with Cl⁻ > OH⁻ selectivity is reported. Selectivity is maintained across lipid membranes of different thicknesses, whereas for selective mobile carriers the discrimination is strongly dependent on membrane thickness.

A complete account of the total syntheses of scabrolide A and yonarolide is disclosed. Early approaches that failed due to unexpected reactivity are described, which informed the evolution of a successful strategy toward these two natural products.

The band gap of single layer graphene can be opened and regulated by an electrochemically induced brominating addition reaction which has prospective applications in micro–nanoelectronics and may bring about a revolution in Moore's Law in ULSI.

We report molybdenum chloride based novel halide double perovskites of different dimensionalities which show dimensionality dependent magnetic exchange interaction and optical absorption. Dimensionality can be tuned by varying the A-cation.

In this work, we first utilize nanoparticles to yield superhydrophobic surfaces for accurate fluid flow control, and design a CD microfluidic chip integrated with multiplex functions to realize non-destructive information extraction from data DNA.

When linked with a flexible linker, two aromatic helices displaying hydrogen bond donors and acceptors may fold back on each other. They may also generate larger complex assemblies.

From chemical shifts to conversion velocity: real-time NMR spectroscopy using a combination of 1D and 2D experiments can monitor individual enzymatic steps in the sialic acid biosynthesis pathway in rat liver cytosolic extract.

Mechanically flexible single crystals of molecular materials offer potential for exciting new directions in advanced materials design. Unravelling the mechanisms of this fascinating bending phenomenon is needed and developed here.

Through simple synthetic modifications, the indigo dye becomes an efficient red-light photoswitch – now also in the solid state.

3-Pyridylcarbinol ester derivatization introduces a universal probe for cryogenic gas-phase infrared spectroscopy of fatty acids that enables assignment of the position and configuration of carbon–carbon double bonds even in the presence of isomers.

Crystallographic, spectroscopic, and computational studies on diiron(II) hydride complexes reveal rapid hydride motions that cause major changes in the electronic structures of the iron sites.

Activated effector caspases 3, 6 and 7 are responsible for cleaving a number of target substrates, leading to the ultimate destruction of cells via apoptosis.

Introduction of a surface defect on a POV-alkoxide imparts both structural and electronic alterations, resulting in “switchable” PCET regiochemistry. Such features provide insight into PCET reactivity at metal oxide surfaces.

Reported here is the catalytic enantioselective desymmetrization of calixarene skeletons for the construction of inherently chiral calixarenes through a transannular arene–arene dehydrogenative coupling reaction.

A ball-milling approach allows the efficient activation of unactivated manganese metal and thus makes the direct generation of arylmanganese nucleophiles feasible without the need for complicated pre-activation processes and metal additives.