Themed collection 2024 ChemSci Pick of the Week Collection

O₂ is an attractive oxidant but it is also kinetically inert which limits its use in synthetic transformations. Metal–ligand cooperativity is a promising biomimetic strategy to activate O₂ for oxidative reactivity and catalysis.

This perspective highlights the challenges and opportunities in achieving sustainable plastic recycling under mild conditions by imitating the active sites and the substrate-binding clefts of enzymes.

An overview of PVC functionalization through the lens of chemical recycling.

Combining organic crystals and polymers results in a new class of all-organic, lightweight, flexible materials with unprecedented mechanical robustness, resilience, and diversity in combination with other functional materials.

Deuteration suppresses the weakly temperature dependent internal conversion (IC) and turns dibenzoterrylene molecules into bright single photon emitters, in agreement with the predictions of the well-known energy-gap law.

Our generative AI model designs copolymers taking their complex hierarchical structure into account. We design the monomer chemistries, stoichiometric ratios, and chain architecture together, and optimise towards a desired property portfolio.

Dithienoarsinines, the first π-extended arsabenzenes, exhibit high stability and planarity. Their structure, optical/electronic properties, reactivity, and coordination behavior are comprehensively studied, highlighting the features of arsenic.

The accuracy of wave function and DFT methods for spin-state energetics benchmarked against curated experimental data of transition metal complexes.

A unimolecular three-helix bundle aromatic foldamer in which each helix interacts with the two others was designed by stepwise transformation of a parallel trimolecular three-helix bundle.

Chiral ionic organic single-crystal (CIOC) were prepared for the first time via ionic self-assembly using organic anions and cations. Interestingly, the CIOC can be ultrasonically exfoliated to 2D nanosheets and exhibit enhanced enantioseparation.

We report the first non-d⁰ Re(V) alkylidyne complex capable of effecting alkyne metathesis at room temperature, featuring air/moisture stability, broad functional group compatibility, and scalable synthesis.

Leveraging multimodal large language models (MLLMs) to process multimodal data inputs and complex inter-modality data dependencies for automated (electro)chemical data mining from scientific literature.

Molecular solar thermal energy storage route using teralylenes with pyridine protonatable moieties for on-demand energy release achieved upon protonation with catalytic amounts of acid.

Alternating copolymerization of a helical polycyclic heteroaromatic with another conjugated unit possessing different electronic characteristics tuned the energy levels and the compatibility with organic salts.

Naphthalenyl- and anthracenylpyridine cyclometalating ligands bind to Pt in different ways, which can be used to tune their emissive properties.

Cu(I) sites enhance their activity upon coordination with oxygen-donor ligands, as demonstrated by infrared photodissociation spectroscopy and ab initio calculations.

Herein, we present a new computational methodology that unlocks the prediction of the complex multi-species multi-equilibria processes involved in the formation of complex metal-oxo nanoclusters.

The asymmetric electrolysis cell concept was introduced to simultaneously produce quinone-based redox-active molecules and high-purity hydrogen gas.

This study explores the mechanisms of photoactivation and radical formation during 3D laser printing using photoresists with a DETC photoinitiator. The role of DETC in high triplet states during radical polymerization is revealed.

The kinetics study herein experimentally demonstrates that an inner-sphere ET mechanism is involved in the conversion of triplet O₂ into a powerful oxidant by an RS–Fe complex. Hydrogen-bond donors are shown to destabilize the transition-state.

Incorporating mixed flexible-rigid backbones into molecular junctions can dynamically block tunneling currents and enhance rectification.

X-ray absorption spectroscopy and variable temperature magnetometry show evidence of 4f-orbital mixing in Cp′₃Eu, which increases its magnetic susceptibility.

This work presents a direct site-selective oxygen–sulfur substitution method that enables transforming polyoxometalates [XW₁₂O₄₀]⁴⁻ (X = Si, Ge) to Keggin-type polyoxothiometalates [XW₁₂O₂₈S₁₂]⁴⁻ using sulfurizing reagents in an organic solvent.

Novel approach combining graph neural network and the physically motivated functional form of an implicit solvent model enables the description of solvation effects with the accuracy of explicit solvent simulations at a fraction of the time.

The dimerization of nitrogen monoxide (NO) is highly relevant in biochemical and environmental redox processes. Here, it is shown how structral constraint and element-ligand cooperativity can steer this reaction.

Bench-stable 3,3-difluoroallyl sulfonium salts proved to be versatile fluoroalkylating reagents for site-selective S-gem-difluoroallylation of cysteine residues in unprotected peptides. The newly added functional groups are poised for ligation.

Neutral inverse-sandwich rare-earth metal complexes of the parent benzene tetraanion with an [M³⁺–(C₆H₆)⁴⁻–M³⁺] core electronic structure were synthesized and characterized. They behave as a four-electron reductant to reduce unsaturated substrates.

The construction of a quadrane scaffold by β-terrecyclene synthase via Coates' route is demonstrated through mutagenesis and isotopically sensitive branching studies. Subsequent enzymatic modifications convert β-terrecyclene into terrecyclic acid.

A tricyclononene and tricyclononadiene monomer library is studied experimentally and computationally to deepen understanding of structure propagation rate relationships in ROMP. A novel poly(tricyclononadiene) post-ROMP functionalization is explored.

How a peptoid binds to a protein was revealed by a co-crystal structure and systematic physicochemical studies.

We show that weaker acid catalysis has profound effects on the dynamicity of vinylogous urethane based polymer networks. Moreover, the dynamicity could be adjusted by changing electronic and steric parameters in the catalytic environment.

A bent azide intermediate is key to form 1-azido-1′-nitrenoferrocene from 1,1′-diazidoferrocene, as shown with UV-pump–mid-IR-probe transient absorption spectroscopy and density functional theoryTD-DFT calculations including spin–orbit coupling.

A high-throughput single-cell MS platform that can perform both lipid profiling and unsaturated lipid CC location isomer resolution analysis was developed, which can be effectively used for in-depth structural lipid metabolism network analysis.

Efficiently merging low-cost high-throughput screening and characterisation, automated data analysis, computational modelling, and cagey – a custom database analysis tool, enhances large-scale data curation and accelerates discovery of organic cages.

A protein-based model of carbon monoxide dehydrogenase displays distinct X-ray absorption, EPR, and vibrational signatures upon CO and CN⁻ binding that support ligand-dependent electronic rearrangement throughout the nickel–iron–sulfur core.

N–N bond formation in octahedral, terminal d¹ Mo(V) nitridos to give μ-dinitrogen complexes requires one eletron oxidation with 0.5 equivalents of oxidant to open a kinetically feasible ambiphilic nitrido coupling pathway.

Simulations reveal that both charge and exciton delocalisation can significantly improve the efficiency of charge generation in organic photovoltaics and explain the failure of classical hopping approaches.

We designed a covalent organic framework (TA-PTO-COF) as a dual-active-center cathode. This work presents a promising organic cathode material for a high-performance aqueous zinc-ion battery.

Simple structural modifications significantly boost the photochromic performance of imine-based photoswitches. This work lays a foundation for exploring new motifs in light-addressable dynamic combinatorial chemistry.

Silylation of iron-alkyl-dinitrogen complexes gives high-spin iron(IV) products that also have an iron(II) resonance structure. The stability and reactivity of these compounds depends on the alkyl group, with insertion and homolysis observed.

The air–water interface is not the site for H₂O₂(aq) formation; instead, it takes place at the solid–water interface.

PoseBusters assesses molecular poses using steric and energetic criteria. We find that classical protein-ligand docking tools currently still outperform deep learning-based methods.

ZIF-8 vaccine enhances the humoral immune response through sustained antigen exposure to the immune system whilst zinc adjuvants the vaccine via inducing T cell activation.

A series of poly(ester-b-carbonate) electrolytes are prepared by a one-pot procedure and structure–property relationships are observed. The polymer was used as a composite cathode binder with excellent discharge capacity and capacity retention.

Our self-evolving graph neural networks for predicting solubilities reconciled different magnitudes of errors and uncertainties of experimental and computational databases, maximizing the database size and the model’s prediction accuracy.