High-entropy alloys offer a huge variety of multielement active sites on a single catalytic surface. This special polyelemental arrangement implies several different fundamental concepts in structure–activity correlations compared to traditional electrocatalysts, which are summarised and their implications for the possibility to adjust the catalytic properties with different limitations are discussed in detail.

This Review describes recent advances in the electrochemical potential-driven preparation of nanometric molecular films of various molecules on technologically relevant substrates, including non-magnetic and magnetic electrodes to investigate the stimuli-responsive charge and spin transport phenomena. We hope to encourage the design of a facile and efficient route for molecular optoelectronic and flexible electronic applications.

A strategy that narrows the interlayer distance of cobalt diselenide (CoSe₂) is reported, which enables strong coupling between CoSe₂ monolayers. The strongly coupled CoSe₂ can catalyze electrosynthesis of H₂O₂ in acidic media efficiently, which yields Faradaic efficiency of 96.7 %, current density of 50.04 mA cm⁻², and product rate of 30.60 mg cm⁻² h⁻¹, outperforming all catalysts reported previously in acidic environments.

A kagome network on the Ag(111) surface hosts guest molecules with enantiomeric selectivity. Each larger pore confines a single guest molecule. The punctuated pirouette of the guest molecule in this confined space is unravelled by a combination of density functional theory and variable temperature scanning tunnelling microscopy in real time at the single molecule level.

The ordered arrangement of terephthalate and fumarate linkers over the fcu net produces a zirconium-based MOF Zr₆(BDC)₃(Fum)₃ with two distinct windows and multiple guest diffusion pathways. This phase is formed by single-step synthesis in a narrow region of the available chemical space, and its identification required a large set of synthetic experiments that were facilitated by automated high-throughput methods.

Sink/float magnetic immunoassays detect proteins, antibodies, and bacteria in samples using a simple mix-and-observe protocol that uses a biofunctionalized small sphere, some liquid reagents and a small permanent magnet. A simple sink/float test of the sphere identifies if the analyte is above or below a predetermined level; the sphere sinks only if the analyte is above the concentration level.

Non-hydrogenative parahydrogen hyperpolarization allows the detection and quantification of α-amino acids down to sub-micromolar concentrations. This method can also be applied to aqueous mixtures after dilution with methanol without any additional sample treatment. This direct approach was tested on human urine, allowing a well-resolved detection of amino acids despite the complexity of the mixture.

Structural snapshots and mechanistic investigation of a key spiroketal synthase provide insights into extensive oxidative backbone rearrangements and spiroketal pharmacophore assembly in rubromycin biosynthesis.

We report a rod-like sulfonated viologen (R-Vi) anolyte for aqueous redox flow batteries (AORFBs). R-Vi possesses a low membrane-penetration rate of ≈10⁻¹⁰ cm² s⁻¹ and the lowest redox potential of −0.55 V vs. SHE among one-electron-storage viologens in AORFBs simultaneously. The R-Vi-based AORFB exhibits an extremely low capacity-fade rate of 0.007 % per cycle in 3200 continuous charging–discharging processes.

A divergent synthesis of skeletally distinct arboridinine (1) and arborisidine (2) was achieved. The central divergent strategy was inspired by the divergent biosynthetic cyclization mode of arboridinine (1) and arborisidine (2) and their hidden topological connection.

Helically folded supramolecular polymers with a high internal rigidity undergo non-uniform unfolding upon UV-irradiation, affording topological block nanofibers consisting of two distinct domains with helically folded and unfolded structures.

We report an alkaline phosphatase (ALP)-responsive lysosomal membrane permeabilization (LMP) inducer, which can specifically accumulate in cancer cell lysosomes for evoking immunogenic cell death (ICD) and converting immunologically cold tumors into hot tumors.

The first osmium-catalyzed electrooxidative C−H annulation is disclosed. While improved selectivities are possible, unprecedented osmium intermediates are presented along with detailed kinetic studies, which revealed the working mode of osmaelectrocatalysis.

This is the first study to use a molten-salt-assisted electrochemical etching (MS-E-etching) method to synthesize Ti₃C₂Cl₂ without metallic impurities. The T_x surface terminations could be in situ modified from −Cl to −O and/or −S in this one-pot process. The obtained −O-terminated Ti₃C₂T_x electrode exhibited a significant increase in capacity.

The gold-catalyzed biscyclization of hydroxyisobutyryl (Hib)-protected aminoallenynes was promoted by BrettPhosAuNTf₂ in the presence of iPrOH to give 1,2-dihydrobenzo[cd]indole derivatives, some of which were converted into nitrogen-containing polycyclic aromatic compounds with highly conjugated π-electron systems. A hexacyclic indolium salt (see structure) showed concentration-dependent photophysical properties attributable to aggregate formation.

Flower-like particles of a redox-responsive liquid crystalline mixture prepared by precipitation polymerization are reported. The influences of monomer composition, polymerization temperature, and solvent on the particle shape are investigated. The shapes formed in the early stage of polymerization remain unchanged. Under reducing conditions, the flower-like particles are degraded much more rapidly than the spherical particles due to their higher surface-to-volume ratio.

Quinones are used for quantitative UV/CD sensing of the concentration and enantiomeric excess of more than thirty aliphatic and aromatic chiral amines, amino alcohols and amino acids. The integration of redox switching into the sensing protocol allows spectral deconvolution of otherwise overlapping CD spectra that are obtained with challenging compound mixtures.

Through rational molecular design, simple chemical synthesis, and structure–property computation analysis, a new catholyte with high potential, two-electron transfer, and high solubility is developed for non-aqueous redox flow batteries.

Hierarchical micro- and nanostructures made of π-conjugated molecules are not yet reported due to the weak control over intermolecular interactions and little-known complex assembly behavior of organic species. Hyperbranched microwire networks comprising binary organic arene-perfluoroarene cocrystals were created, which show optical waveguiding and light-harvesting abilities.

The reaction product between the bulky FmesBH₂ borane and an isonitrile serves as a B/N frustrated Lewis pair that adds nitriles to form the dihydro-1,4,2-diazaborole heteroarene derivatives. One example of this class of compounds was shown to undergo a cycloaddition reaction with N-phenylmaleimide.

A crystalline carbazolylaluminylene with a monocoordinated aluminium atom featuring a lone pair of electrons and two vacant orbitals has been isolated at room temperature. The coordination behavior of this aluminylene towards transition metal centers is shown to afford a series of novel aluminylene and alumanyl complexes with diverse coordination modes in a one-step process.

An aryl radical activation strategy has been developed that can engage unactivated alkyl iodides in copper-catalyzed Negishi-type cross-coupling reactions. The strategy is based on the largely overlooked yet highly efficient reactivity of aryl radicals to abstract iodine atoms from alkyl iodides.

An oil–water–oil triphase method based on a phase engineering strategy is developed for the bottom-up synthesis of ionic covalent organic framework nanosheets (iCOFNs). A favourable reaction region with moderate monomer concentration is achieved in the middle water phase. The resulting three cationic and anionic iCOFNs show potential for ultrathin biogas separation membranes.

Safety is always a topic of concern after reports of devices catching fire due to battery failure. Using non-flammable electrolyte as an ultimate solution is difficult to be applied to commercial batteries because of various problems such as poor compatibility, high viscosity and so on. Here, we report a non-flammable electrolyte with excellent comprehensive performance, and applied it to sodium-ion pouch cells with different promising materials.

Splitting of water by a single vanadium is greatly facilitated by a C₆₀ support, which can be regarded as a small piece of porous carbon nanomaterials, especially those with intrinsic pentagonal defects and curvatures. The compelling experimental and theoretical evidence demonstrates the important role of support in single vanadium atom catalysis.

The escape of surface oxygen and Li-insulator Co₃O₄ formation are the main causes for the capacity fading of 4.6 V LiCoO₂ cathode. The oxygen escape is significantly inhibited by tailoring the Co3d and O2p band centers and enlarging their band gap with MgF₂ doping, which enables a stable cycling of 4.6 V LiCoO₂ cathode.

A strategy toward the optimization of photothermal conversion materials with broad optical absorption and high conversion efficiency via the d-d interband transitions is demonstrated. The high-entropy-alloy nanoparticles could realize an excellent solar harvesting performance especially compositing with up to seven 3d elements in a single phase, ascribing to the fully filled energy regions below and above the Fermi level.

A two-dimensional coordination polymer (Ni₃BHT) demonstrates rapid and reversible intercalation of both cations and anions in an electrochemical capacitor (EC). This first observation of dual-ion intercalation in ECs presents a unique scenario, wherein cation intercalation in Ni₃BHT is pseudocapacitive but anion intercalation is capacitive in nature.

Iridium clusters stabilized surface reconstructed oxyhydroxides on an amorphous metal boride array are reported, achieving an ultralow overpotential of 178 mV at 10 mA cm⁻² for OER in alkaline medium. The coupling of iridium clusters induces the formation of high-valence cobalt species and Ir–O–Co bridges between iridium and oxyhydroxides at the atomic scale.

Two D-A-type covalent organic frameworks have been designed and prepared following a novel strategy for the construction of endurable and reliable memory devices. The state-of-the-art memristor-based COF-TT-BT thin film showed typical rewritable resistive switching behavior, a high ON/OFF current ratio (ca. 10⁵), good endurance of 319 cycles, and a long retention time of 3.3×10⁴ s.

Guest-driven light-induced spin change (GD-LISC) was firstly realized in a Hofmann-type metal–organic framework with photochromic azobenzene guests.

A beryllium-free deep-ultraviolet nonlinear optical hydroxyborate, NaSr₃(OH)(B₉O₁₆)[B(OH)₄] (NSBOH), was constructed by a covalent bond modification strategy via a facile hydrothermal reaction. Moisture-stable NSBOH is SHG-active at both 1064 nm and 532 nm, with deep-UV transparency to wavelengths below 190 nm, and good phase-matchability in the near deep-UV region, a rare combination for NLO hydroxyborates.

Phototuning the turning-off and the polarization inversion of circularly polarized luminescence signals is obtained in the corresponding photostationary state of the same helical cholesteric superstructure constructed from the light-driven hydrogen bonded chiral fluorescent molecular switch, which derives from the different conversion ratio of Z/E photoisomerization of the switch upon different light irradiations.

A Brønsted acid catalyzed intramolecular hydroalkoxylation/Claisen rearrangement is disclosed that involves an unexpected dearomatization of nonactivated arenes and heteroaromatic compounds and allows the practical and atom-economic synthesis of various valuable spirolactams. Moreover, the asymmetric version of this tandem cyclization is also achieved via kinetic resolution by chiral phosphoric acid catalysis.

An ultrahigh supramolecular cascaded RTP-capturing system was constructed based on a multivalent supramolecular aggregate using cucurbit[7]uril (CB[7]) and sulfonatocalix[4]arene (SC4AD) in aqueous medium. Energy transfer from G⊂CB[7]@SC4AD to primary (RhB or DBT) and then to secondary energy acceptors (Cy5 or NiB) gives rise to long-range and long-lived photoluminescence, especially NIR delayed emission (675 nm).

In a biocatalytic approach to the production of fluorinated compounds, halide methyltransferases (HMTs) were found to form fluorinated S-adenosylmethionine (SAM) from S-adenosylhomocysteine and fluoromethyliodide. Although too unstable for isolation, fluorinated SAM was accepted as a substrate by C-, N- and O-specific SAM-dependent methyltransferases (MTs) to enable the fluoromethylation of small molecules (see scheme).

Structurally flexible, copper scorpionate binds ethylene extremely selectively from an ethylene–ethane mixture and displays excellent performance as a reusable material for the important and challenging C₂H₄/C₄H₆ separation.

Amphiphilic random copolymers were employed to construct enzyme nanoreactors for catalysis in an organic solvent. Unnatural selectivity over a range of substrates was introduced by tuning the cross-linking density.

We present an isomerism strategy to study the effect of molecular structures on radioluminescence. Under UV-light excitation, all isomers showed bright phosphorescence with an efficiency of up to 22.8 %. Unexpectedly, both m-BA and p-BA scintillators showed bright luminescence under X-ray irradiation, which was ascribed to both excellent electrical conductivity and efficient suppression of non-radiative decay.

As one of the most ubiquitous bulk reagents available, THF is activated by visible light irradiation of quantum dots in a direct, site-selective and redox-neutral manner. The resultant α-oxyalkyl radicals, generated from α-C−H of THF on the surface of QD, enable either coupling with the α-amino radical of amines, or addition to chromones and terminal alkynes.

The uncharged univalent and reactive nitrene is captured and stabilized by silylenes. Two nitrene compounds are synthesized and fully characterized. The nitrene character was established by X-ray analysis, first-principles electronic structure studies using density functional theory, and natural bond orbital-based bonding analysis.

Two n-type conjugated polymers with different backbones and a n-type dopant 1,3-dimethyl-2-(3,4,5-trimethoxyphenyl)-2,3-dihydro-1H-benzo[d]imidazole (TP-DMBI) are synthesized, and electron mobility of 0.53 cm² V⁻¹ S⁻¹, electrical conductivity of 11 S cm⁻¹ and power factor 32 μW m⁻¹ K⁻² for n-type organic thermoelectrics are achieved by TP-DMBI doped films, which out-perform N-DMBI doped films.

Presented herein are detailed ^1/2H and ¹³C pulse EPR and DFT investigations of an S=1/2 terminal iron–carbene species. These studies reveal substantial spin density localized at the carbene-bound Fe center, in contrast with what has been reported to date for radical metal–carbenoid species. The {Fe=C(H)Ar}¹¹ complex serves as a well-defined reference compound for comparison to data reported for in situ trapped intermediates.

An unprecedented NiH-catalyzed enantio-, regio-, and anti-selective intramolecular coupling of alkynones to construct O-, N-, S-containing endocyclic allylic alcohols was developed. The choice of metal precursors plays a key role in tuning the regio- and enantio-selectivity. This study offers a new anti-hydrocyclization mode for enantioselective hydrofunctionalization of alkynes.

Radical–radical chain reactions may contribute to rapid growth of polycyclic aromatic hydrocarbons in combustion and astrochemical environments. Phenyl and benzyl radicals were experimentally observed to complete this chain reaction, producing diphenylmethyl and triphenylmethyl radicals by prompt H-atom loss (see scheme). This observation confirms the plausibility of such chain reactions at high temperature and low pressure.

The first synthesis of (±)-Setigerumine I, an isoxazolidine Papaveraceae alkaloid, is realized through a biomimetic strategy. The synthesis sheds light to the possible biosynthetic origins of these elusive natural product family members.

The catalytic asymmetric synthesis of P-chiral phosphorus compounds is an important way to construct P-chiral ligands. Herein, we report a new strategy that adopts the pyridinyl moiety as the coordinating group in the cobalt-catalysed asymmetric nucleophilic addition/alkylation of secondary phosphine oxides (SPOs). A series of tertiary phosphine oxides (TPOs) were generated with up to 99 % yield and 99.5 % ee, and with broad functional-group tolerance.

A kinetic resolution of rac-secondary phosphine oxides via the enantioselective P-benzylation process catalyzed by the palladium/Xiao-Phos was designed. Both, tert- and sec-phosphine oxides were delivered in good yield and excellent enantiopurity (selectivity factor up to 226.1). The synthetic utilities are further demonstrated by the facile preparation of several P-chiral compounds, precursors of bidentate ligands, and transition metal complexes.

Pyrazol-4-ylidenes, a type of mesoionic carbenes, also named cyclic-bentallenes (CBA), can be more basic than Verkade proazaphosphatrane and even Schwesinger phosphazene P₄(^tBu). With these results it is demonstrated that carbenes should not be overlooked as neutral purely organic superbases.

Metal-organic frameworks (MOFs), especially MOF nanosheets (NS), are very good candidates for photocatalysis. In this work, two types of donor–acceptor MOF NSs were prepared, including an acceptor-on-donor NS and a donor-on-acceptor NS. It was found that the acceptor-on-donor NS type has very good performance even with fewer catalytic centres. This may help future research to design photocatalysts.

A modular synthetic approach paves the way to nanoscale platform molecules for supramolecular graphite surface patterns at the solid–liquid interface. While a perylene dye bound at the end of the pillar remains fixed above the molecule center and points into solution, a fullerene ester bound at the same position performs a tumbling motion that translates as a “haze” in the otherwise submolecularly resolved images.

The generation of FSO₂ radicals under electrochemical conditions is reported. Various sulfonyl fluorides and heterocycles, including a novel oxathiazole dioxide heterocycle, can be obtained in good to excellent yields. Some β-keto sulfonyl fluorides and derivatives showed potent activities against Bursaphelenchus xylophilus and Colletotrichum gloeosporioides.

The novel inhibitor NADH-OH binds with high affinity to respiratory complex I, thereby blocking NADH oxidation and the production of reactive oxygen species. The tight interaction is mediated by residues conserved in complex I but lacking in other enzymes containing a Rossmann-fold. Accordingly, it is a lead structure for the development of new drugs for fighting oxygen stress.

We reported the nuclear-spin driven magnetization dynamics involving both metal ion and the ligand, for first time, in two Ho^III isomorphic single-molecule magnets, where the behavior is originated from the super-hyperfine interaction related to the difference in nuclear spin number of protium (I=¹/₂) and deuterium (I=1).

A highly efficient, versatile and atom-economic protocol to chiral allylic phosphine oxides is demonstrated via palladium-catalyzed asymmetric hydrophosphinylation of allenes with phosphine oxides. A family of chiral allylic phosphine oxides with a diverse range of functional groups were obtained in high yield (up to 99 %) and enantioselectivities (up to 99 % ee).

An amine–carboxylic acid C−C coupling would be a valuable addition to the synthetic toolbox of carbon–carbon bond-forming reactions. Using miniaturized high-throughput experimentation, we have developed the first amine–acid cross-coupling to form C(sp³)−C(sp³) bonds based on preactivation of the building blocks and nickel catalysis.

Formamidinium (FA)-based additives in precursor solutions suppressed the formation of the undesired δ phase during the crystallization of FAPbI₃ perovskites, and heat-induced permeation of 4-tert-butylbenzylammonium iodide (tBBAI) into inner perovskite grains stabilized the α structure. Solar cells assembled from this material exhibited improved power conversion efficiency and stability.

Two successive asymmetric reductive aminations (ARAs) have been merged into one reaction system to generate enantiopure C₂-symmetric secondary amines. The iridium-phosphoramidite complex successfully manages the dual ARAs by using two distinctly different types of amine sources: an inorganic ammonium salt and an organic primary amine.

Quantum confined nanosheets (NSs) of 3D perovskites with a thickness of two lead halide layers can be prepared by using the dodecylammonium/tosylate ligand pair. The addition of Eu-nanodots to the colloid prevented the NSs from a structural rearrangement and/or coalescence. Deep blue-emissive colloids were recovered by simply dispersing it in toluene.

A new perfluoro-tert-butylation protocol debuts: Consecutive triple fluorinations of 1,1-dibromo-2,2-bis(trifluoromethyl)ethylene (DBBF) generate (CF₃)₃C⁻ species, which enables efficient nucleophilic perfluoro-tert-butylation of various electrophiles. The C(CF₃)₃-containing products can be successfully applied in ¹⁹F-magnetic resonance imaging.

A Zn/Fe-bimetallic metal-triazolate framework (MET) modified with 4,5-dichloroimidazole (dcIm) was used to prepare the Fe single-atom catalyst FeN₄Cl₁/NC. In the oxygen reduction reaction (ORR), the catalyst offers fast mass transfer and high catalytic activity because of abundant mesopores (pore:volume ratio 0.92), a high Fe loading (2.78 wt %), and defined FeN₄Cl₁ sites with a distinct electronic structure.