Themed collection 2024 Chemical Science HOT Article Collection

Catalysts consisting of isolated metal atoms bonded to solid supports have drawn wide attention by researchers, with recent work emphasizing noble metals on metal oxide and zeolite supports.

Over the years, spectroscopic, electrochemical and structural studies of [FeFe] hydrogenases have provided ‘pieces’ of information to complete the ‘puzzle’ of their catalytic cycle. However, there are still missing pieces that we need to fill in.

An overview of the recent advances in the photoinduced construction of axially chiral compounds was presented.

Photoswitching via indirect excitation allows harnessing low-energy photons to control molecular configuration. Herein, the state of the art of the predominant indirect photoswitching methods is presented.

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.

While chemistry has a role as the central science, other sciences are also central to solving the problems that lie ahead. To be more effective in this endeavor, we need to connect disciplines and break down the silos that artificially separate them.

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.

Recent progresses in Cu–oxygen adducts towards recalcitrant C–H activation are reviewed with focus on Cu metalloenzymes and bioinspired synthetic models, mono- to polynuclear complexes, working under homogeneous and heterogeneous catalytic conditions.

Adamantane-type clusters exhibit a huge diversity of chemical compositions, structural details, and resulting properties.

Recent progress of preparation approaches for HCs is systematically overviewed, with a special focus on the comparison between traditional fabrication methods and advanced strategies regarding their influence on performance.

Recent advances and present status of 3D-printed micro-batteries with respect to the connection between printable materials and printing techniques, as well as the rational design considerations are summarized.

In response to societal developments and the growing demand for high-energy-density battery systems, alkali metal batteries (AMBs) have emerged as promising candidates for next-generation energy storage.

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.

The acidic redox-assisted deposition (ARD) of cobalt manganese oxyhydroxides (CMOH) as a solid-state inorganic binder has been demonstrated. CMOH is stable and highly adhesive under high oxidative currents during OER tests.

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.

A pair of CP-MR-TADF enantiomers with high-order B,N-embedded hetero[8]helicene, (P/M)-BN-TP-ICz, was constructed. CP-OLEDs exhibit narrow green emission peaking at 540 nm with maximum EQEs of 32.0% and g_ELs of approximately 7.70 × 10⁻⁴.

Diversify your bonds! The reactivity of preactivated cycloalkynes in the retro-Cope elimination reaction was quantum chemically investigated. Based on our finding, we rationally designed a suite of next-generation reagents.

Generation of stannylpotassium using silylstannanes and its application to stannylation of aryl halides have been developed.

Metal–arene contacts in divalent rare earth complexes can give rise formal 4fⁿ d(_x²−y²) valence electron configurations where metal–arene δ-bonding modulates the electronic structure. Rare earth ions without d-contribution (i.e. fⁿ⁺¹) are unaffected.

The template complex of a zinc porphyrin nanoring forms several pseudopolymorphs featuring different conformations of the π-system. The metal-free nanoring is even more flexible, and adopts an elliptical geometry when co-crystallized with C₆₀.

Helically chiral MR-TADF compounds tBuPh-BN and DPA-tBuPh-BN show narrowband circularly polarized luminescence that translates into high-performance hyperfluorescent organic light-emitting diodes.

Pseudomonas from Enigma Lake (Antarctica) has a peculiar lipopolysaccharide with an unusual tendency of decreasing lipid A secondary hydroxylation. This results in increased membrane fluidity that ensures bacterial survival at near-zero temperature.

Combining dimer pair calculations and coarse-grained modelling to predict the solid-state phase behaviour of porous organic cages and build design principles for introducing chirality into achiral cages.

An antiaromatic buckybowl and two doubly curved nanocarbons by fusion of nonbenzenoid rings onto pyrene have been synthesized and characterized.

Using a combination of experimental and computational tools, two compounds were discovered in the well-studied BaO–Y₂O₃–SiO₂ phase field.

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

A new structural type in dinitrogen chemistry has been obtained by the attempted one electron reduction of a bridging (NN)²⁻ complex of scandium.

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

Contrasting donor : acceptor pairs were constructed to study the non-radiative decay of red exciplexes. On applying a new strategy to suppress energy loss, the proof-of-concept emitter allowed the red OLED to achieve a maximum efficiency of 23.8%.

We have synthesized β-diaryl-β-hydroxyl-α-amino acid derivatives through radical addition-type aldol reaction, which was confirmed by spectroscopic experiments, control experiments, and DFT calculations.

We zoomed in on the SARS-CoV-2 interaction layers in open and closed states, revealing a protein–solvent–glycan polarization network supporting the open state. Besides, we showed that the glycan shield maintains viral camouflage in both states.

Bench-stable trityl isocyanide enables the photoredox catalytic cyanation of carboxylic acids, alcohols and alkyl halides.

A cost-effective and high-performance composite membrane is developed by leveraging a localized high iodine concentration layer based on the adducts chemistry, where polyiodide shuttling can be suppressed with improved coulombic/energy efficiency.

A bifunctional molecule with binders for calmodulin (CaM) and glutathione S-transferases (GST) converts GST into a triggerable enzyme, whose activity is unnaturally regulated by CaM's conformational state and consequently, by calcium ions.

Nucleic acids with hypermodified nucleosides perform stereoselective RNA/DNA-mediated peptide coupling, followed by thermal release of the peptide, leading to temperature-driven one-pot cycles with gradual homochiral L-peptide enrichment.

A green MOF phosphor can maintain 84% of its initial emission intensity after being heated to 150 °C, exceeding several commercial inorganic phosphors.

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.

Stereogenic-at-iron complexes, featuring strongly σ-donating mesoionic carbene (MIC) ligands, exhibit enhanced catalytic efficiency compared to their normal N-heterocyclic carbene congeners in nitrene-mediated ring-closing C(sp³)–H amidations.

Atomically precise Au₃₆(SR)₂₄ clusters can provide a unique reaction pathway for nitrobenzene hydrogenation navigated over a cluster catalyst, thereby achieving an exclusive selectivity for p-aminophenol.

The first example of CO₂-adsorption actuated spin transition tuning in a 2D Hofmann-type framework is demonstrated, where effective spin-state stabilisation is disseminated as the CO₂ occupation rate in the framework based on gating temperature.

Symmetry-breaking approach exceeds the sensitivity of the vibrational Stark effect. Nitrile groups report on microscopic electric fields without interference from hydrogen-bonding interactions.

A built-in electrophilic/nucleophilic domain promoted the favorable adsorption of urea molecules on the surface/interface of heterogeneous Ni₂P/Ni₃N, reducing the energy barrier of the rate-determining step, and boosting urea electrolysis.

A new method for analyzing crystal structures of molecules distorted from their regular shape separates atom movements into symmetry modes so that molecular conformation of functional materials can be quantified and compared easily across databases.

Resonant X-ray diffraction measurements were used to examine Cu site differentiation within a Cu₄S cluster that distorts its geometry to activate N₂O, thus mimicking the behavior of the biological Cu_Z active site.

Vacuum ultraviolet excitation of CO₂ clusters and concomitant energy transfer to naphthalene leads to ionization which provides an understanding of excited state chemistry relevant to astrochemistry.

The introduction of Ni(dmgH)₂ as a cocatalyst with CsPbBr₃ quantum dots facilitates the activation of molecular oxygen to superoxide radical, initiating radical catalyzed C–N coupling between aldehyde and amine to form amide.

Electronic modulation and lattice strain in pre-lithiated electrocatalysts, lead to optimized Li–O intermediate adsorption and enhanced electron transfer for improved Li–O₂ battery performance with high efficiency, longevity, and large capacity.

Alzheimer's disease (AD) is one of the most fatal and irreversible neurodegenerative diseases, which causes a huge emotional and financial burden on families and society.

2D monolayer, bilayer, sandwich bilayer, four-layer, multi-layer and chiral bilayer supramolecular networks were constructed from tetrapyridine functionalized pillararene and Co(II) and Cu(II) through controlling the temperature and guest induction.

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 application of trichloroacetyl isocyanate (TAI) adducts as initiators of copper-mediated reversible-deactivation radical polymerization (Cu-RDRP) unlocks straightforward access to complex polymeric architectures with ultra-high chain density.

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.

The concise total synthesis of ngouniensines is reported, in which 2-Me-tryptamine undergoes sequential C–H functionalization with different aldehydes to afford the azepino[4,5-b]indole core and an exocyclic conjugated alkene, respectively.

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.

Herein, intensified electrochemiluminescence (ECL) and photoluminescence (PL) via supramolecular anion recognition interactions are demonstrated. This great improvement is attributed to the restriction of intramolecular rotation upon anion coordination.

Chemical reactions in millimeter-sized droplets can be accelerated by more than an order of magnitude.

Herein, we report a novel approach to pyrroloiminoquinones which was enabled by the development of a Larock/Buchwald–Hartwig annulation/cyclization cascade to rapidly construct the core, which was further elaborated to 5 of these natural products.

We report the total synthesis of seven Illicium-derived neolignans along with experimental evidence which unites homooligomers and apparent heterooligomers under a new biosynthesis proposal that features a single common precursor.

A conformation engineering strategy is proposed to manipulate the crystal structure of electron deficient heteroarenes for superior n-type organic semiconductors with an electron mobility of 3.5 cm² V⁻¹ s⁻¹.

We achieve a dicarbanion-centered Au₄ cluster and three assembled Au₁₁ (net-like), Au₂₈ (dumbbell-like), Au₁₄ (closed) clusters. Spectral monitoring, kinetic and theoretical investigations reveal four structure-dependent distinct catalytic pathways.

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.

A micro–nano spherical spinel LiNi_0.5Mn_1.5O₄ cathode material with highly exposed {111} facets has been designed. This unique structure could inhibit manganese dissolution, facilitate Li⁺ diffusion, and mitigate volumetric strain during cycling.

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.

We introduce planarity breaking as a new design strategy for controlled supramolecular polymerization.

The key structural features that aldehydes should present to favour imines over hydrates in water are investigated at different pD values. Sulfonate ortho-substituents remarkably stabilize iminium derivatives while disfavouring hydrate formation.