A conceptual electronic structure trip from [4n] Hückel antiaromatics to diradicaloids and to more hierarchical complex molecular shapes made by internal covalent hybridization of the peripheral [4n] π-electron circuit is described. Focus is on the underlying physical organic chemistry implications.

Metal–organic framework micro/nanoparticles (MOF MNPs) are reviewed with a focus on their morphological anisotropy, which plays a unique role in producing innovative structures and regulating properties with enhanced performance.

Big (Bio)Chemical Data Mining: Large and complex chemical data sets generated by modern analytical technologies have led to the so-called Big (Bio)Chemical Data era. These data sets can be produced using modern analytical instruments such as multi-dimensional chromatography, high-resolution and multi-dimensional spectroscopy, hyperspectral imaging and DNA/RNA microarrays. Chemometric methods have shown potential to analyze BBCD especially in omics sciences and chemical toxicology/drug discovery.

This Review focuses on molecular catalysts for the electrocatalytic CO₂ reduction reaction (ECO₂RR) including metal bipyridines and macrocycle complexes, and summarizes the molecular engineering strategies developed to regulate the intrinsic catalytic efficiency and modify the electrode. Guidelines are provided for the rational design of ECO₂RR catalytic systems.

Recent developments in strategies for transition-metal-free regioselective C−H borylation are summarized in this Review. Strategies developed to control the regioselectivity of the electrophilic borylation, such as approaches controlled by electronic effects, auxiliaries, and steric factors, are also discussed. EDG=electron donating group, DG=directing group, TM=transition metal.

Fusion of azulene to acenes of various length led to unexpected properties such as aromaticity and photophysical properties, and they are more stable than the respective isoelectronic acenes. Their dications showed aromaticity shift and one of them exhibited open-shell diradical character.

Photoexcited nickel catalysis enabled silyl-radical-mediated activation of carbamoyl chlorides. This process provides an operationally simple and widely applicable amidation reaction of a plethora of aryl and heteroaryl halides. Mechanistic understanding suggests that the reaction involves an energy-transfer mechanism for aryl bromide; while a single-electron-transfer mechanism is operating for aryl chlorides.

A metal-free linkage chemistry of unactivated alkenes and sulfonimidoyl fluorides via hydrosulfonimidoylation to construct sulfoximines within minutes is presented. An intermolecular hydride transfer process is the key step in the reaction.

An unprecedented oxidative radical NHC catalytic system is reported that allows an efficient difunctionalization of olefins for the divergent synthesis of various ketones. Key to success is the use of peroxyesters as “dual-role” reagents to achieve a sequential single-electron oxidation and intermolecular hydron atom transfer.

To promote the sp²-to-sp³ hybridization transformation in ionic crystals, the realization of internal-lattice stress-transfer from ionic groups to covalent groups is proposed. It is demonstrated in a crystal of LiBO₂ which undergoes the transformation at unprecedentedly low pressure of only 2.85 GPa.

An adaptable strategy toward a multi-stimuli-responsive fluorescent material with stage-by-stage responsive behavior was developed. This strategy ensures the compatibility of different stimuli-responses and the adjustability of stimulus-response behavioral logic. These multi-stimuli-responsive fluorescent materials exhibited strong accessibility and adaptability for information encryption.

Metal-organic frameworks (MOFs) with large pores often lack sufficient hydrophilicity and stability. A post-synthetic modification of MOF-808 with di-sulfonic acids simultaneously enhances its hydrophilicity and stability while maintaining the high water-sorption capacity, achieving high swing capacities practical for potential applications, such as water harvesting and adsorptive heat transformations.

Photoetching can confer BiVO₄ with oxygen vacancies and enhance the catalytic performance of BiVO₄. The photoetched BiVO₄ can catalyze water splitting to generate oxygen and hydroxyl radicals under the mediation of ultrasound. The generated oxygen can relieve tumor hypoxia, thereby improving the sonodynamic cancer therapy performance of BiVO₄.

Three types of single-point mutants of Amyloid-β peptide associated with familial Alzheimer's disease were simultaneously identified with aerolysin nanopores assisted by a 3D blockage mapping strategy. This is based on the combination of the conventional current blockage (I_b/I₀), duration time (t_D) and the reliable standard deviation of current blockade fluctuations (σ_b).

Acid resistance (12 M HCl) was made possible for two isomorphic two-dimensional silver-based coordination polymers. Protection is provided by a hydrophobic organic shell and a dynamic proton buffer layer via a thiolate-thione tautomerism of 2-thiobenzimidazole ligands. Thus, these ligands are promising surface inhibitors, acting as a dual protective shield against metal corrosion.

The on-surface synthesis of covalent nickel tetraphenylporphyrin network on Au(111) is studied by a multitechnique approach combining local microscopic insights with space-averaging synchrotron radiation-based methods. Even though the porphyrin nanomesh is not perfectly ordered extending the π-system results in the appearance of energy-dispersive electronic features while the Ni cores remain in the characteristic single-molecule configuration.

Knoevenagel condensation at the methyl groups of a 2,4,6-trimethylpyridine monomer was promoted by in situ acylation of the nitrogen atom, yielding highly crystalline vinylene-linked covalent organic frameworks. The resultant Lewis basic, pyridine-decorated, regular, nanoporous structures catalyzed spatially confined organic esterification with good selectivity.

The nickel catalyzed Suzuki–Miyaura-type coupling of aryl sulfamates and boronic acid derivatives enabled by temperature-controlled mechanochemistry via the development of a programmable PID-controlled jar heater is reported. This base-metal-catalyzed, solvent-free, all-under-air protocol was also scaled 200-fold using twin-screw extrusion technology affording decagram quantities of material.

The influence of branching on polymer self-assembly is investigated by conducting polymerisation-induced self-assembly of sparsely grafted poly(lauryl methacrylate)-graft-poly(benzyl methacrylate) in n-dodecane. Electron microscopy and X-ray scattering techniques are used to characterise the resulting materials.

By using topologically chiral [2]catenanes as not only the chiral platform but also the switching scaffold, the first construction of a novel bidirectional circularly polarized luminescence switching system was successfully realized.

Upon the dephosphorylation of ALP, the leucine-rich phosphopeptides self-assemble into micelles and then convert into nanoribbons. The phosphopeptides/assemblies first aggregate on the cell membrane of osteosarcoma cells, and then enter cells via endocytosis, disrupt the nuclear membrane, and finally accumulate in nuclei by interaction with histone proteins to induce cell death.

Polyoxometalate nanoclusters are used as supramolecular cross-linkers to solidify deep eutectic solvents, which creates semi-solid supramolecular polymer electrolytes with superprotonic conductivity. Upon mild heating, these electrolytes can infiltrate into the voids in supercapacitor electrodes, form highly stable interfaces, and lead to improved electrochemical performance.

We combined covalent organic frameworks (COFs) and piezoelectric material by covalent bonds to form a Z-scheme core@shell heterostructure piezo-photocatalyst with tunable shell thickness for overall water splitting. The optimal sample reveals the unprecedented H₂ and O₂ production rates of 1416.4 and 708.2 μmol h⁻¹ g⁻¹ under the excitation of ultrasonication coupled with visible light irradiation.

Multi-scale chirality evolution was observed from DNA-assembled hybrid chiroplasmonic superstructures comprised of metal nanoparticles and organic chromophores, as a result of distinct fundamental chiral interactions at different hierarchical levels. The findings present new challenges to current theoretical frameworks to describe chiral hybrid systems, and will motivate computational and theoretical advances.

A one-component organosilicon ferroelectric D-chiro-inositol-SiMe₃ is designed by using the chemical strategy of introducing quasi-spherical [-Si(CH₃)₃] groups into D-chiro-inositol. It exhibits stable and electrically switchable spontaneous polarization on the thin film, which has extremely low hardness of 72.8 MPa and small elastic modulus of 5.04 GPa.

A series of highly twisted and fully armchair-edged graphene nanoribbons (AGNRs) have been synthesized by Cu-catalyzed deoxygenative coupling. These twisted AGNRs have lengths up to 2.65 nm and display strong emission with a fluorescence quantum yield up to 81 %.

A special design of anion-trap additive can greatly enhance the stability and capacity of the Zn ion batteries via modulating preferred Zn crystal plane and enabling fast Zn ion migration.

In neutral aqueous solution, a single-atom nanozyme Ni−N₅−C with enzyme-like catalytic active sites exhibited ultra-high current density of 1.2 A cm⁻² and durability of 100 h for electroreduction of CO₂ to CO.

We constructed single-atom Rh embedded on Ti-doped CeO₂, which exhibited record-breaking TOF of 493.1 h⁻¹, 99.1 % ethanol selectivity and outstanding stability in CO₂ hydrogenation. Synergistic effects of Ti-doping and single-atom Rh favor CH_x*/CO* formation and their subsequent coupling into ethanol. Ti-doping-induced crystal reconstruction leads to the stabilization of single-atom Rh site and catalytic stability.

An aza-BODIPY dimer exhibits unique double intra- and intermolecular exciton couplings, resulting in a dramatic red-shift of the absorption to the second near-infrared (NIR-II) region. Its self-assembled nanoparticles have high photothermal conversion ability and are ultra-photostable, which can efficiently lead to complete tumor ablation under 915 nm laser irradiation with ultralow power density.

Catalytic olefin metathesis can be performed in live microalgae, converting the fatty acids stored in lipid organelles to polymer building blocks and chemicals in vivo.

Programmable multivalent DNA nanomaterials are designed through the biomimetic assembly of DNA with Food and Drug Administration-approved protamine, providing biocompatible and stable drug carriers with high avidity in a simpler method. This practical approach achieves sensitive tumor imaging and targeted cancer therapy, and offers new clinical translation opportunities.

Activity-based sensing probes and whole-body photoacoustic imaging have enabled the selective detection of monoacylglycerol lipase (MGL) and fatty acid amide hydrolase (FAAH) activity in the context of obesity and gastrointestinal tract inflammation.

An efficient catalytic asymmetric [2+2] cycloaddition reaction of allenyl imide and alkenes was achieved by utilizing chiral N,N′-dioxide-magnesium(II) complex as the catalyst. This protocol provided a series of axially chiral cyclobutenes in high yields with excellent enantioselectivities. A stepwise mechanism was proposed based on experimental studies and DFT calculations and π–π stacking interaction was crucial for the enantioselectivity.

The isolation and bonding analysis of a series of heterometallic hydride complexes shows they have subtly different bonding geometries. These compounds can be described as snapshots along a continuum of bonding between trigonal and hexagonal planar geometries.

Novel covalent adaptable liquid crystal network (CALCN) actuators crosslinked by dynamic AIE luminogens were built based on Diels–Alder chemistry. This all-in-one material design “visualizes”, through fluorescing, the crosslinking state and actuation capability for actuation-guiding in CALCN, while enabling network “re-bonding” through associative and dissociative exchange mechanisms for unprecedented actuation-reprogrammability.

Sn vacancies have long been thought to be the key defects inducing high p-type self-doping in Sn-based perovskites, such as CsSnI₃. However, by performing rigorous first-principles calculations, it is revealed that the defects dominating p-doping are Cs vacancies instead of Sn vacancies.

Photogenerated electrons and holes in CdS hollow spheres loaded with MoS₂ and MoO₂ dual cocatalysts are applied to hydrogen evolution and selective pyruvic acid production, respectively. This bifunctional strategy can fully utilize the redox abilities of photogenerated electrons and holes to enhance photocatalytic activity.

In the NLO materials reported herein, an electron transits from the oxygen atom of the valence state to the barium atom of the conduction state caused by the optical excitation. The charge transition generates instantaneous spatial dipole moments, which contribute to the projected SHG. Depending on the arrangement and ambience of the dipole moments, all microscopic SHG integrate into the macroscopic SHG response.

We report a synergistic interface bonding strategy to construct novel flexible fiber-shaped composite cathodes, in which polypyrrole@sulfur (PPy@S) nanospheres (≈500 nm) are homogeneously implanted into the built-in cavity of self-assembled reduced graphene oxide fibers (rGOFs) by a facile microfluidic assembly method. The PPy@S/rGOFs cathode exhibits good mechanical property, excellent electronic conductivity and enhanced cycling performance and outstanding high-rate capacity.

A metal-free, photosensitized regioselective diamination of alkene is reported. The keys to this advance are: 1) rational design of bifunctional diamination reagent, 2) simultaneous generation of long-lived iminyl radical and transient amidyl radical with significantly differed reactivities, and 3) involvement of photoinduced energy transfer reaction mode.

Heteroleptic metal-organic cages are prized for their structural complexity and multi-functionality. Controlling integrative self-sorting processes necessary to achieve defined self-assembly of these supramolecular hosts is a significant design challenge. In this work, ligand-tethering strategies are described that allow access to metal-organic cages with highly anisotropic cavities described by two inequivalent, unsymmetrical ligand scaffolds.

A reversible fluorescent redox probe with emission beyond 1500 nm was synthesized to dynamically monitor the time-resolved reactive oxygen species (ROS) fluctuations during hepatic ischemia-reperfusion injury (HIRI) in vivo. The strategy not only circumvents the difficulty in building reversible fluorescent probes in the NIR-II region but also offers a useful tool for early diagnosis and timely treatment of HIRI.

The boron acid additive can alleviate the intrinsic tradeoff between Zn nucleation/dissolution kinetics and the interfacial hydrogen evolution reaction by modulating the solvation sheath. The formed solvation structure with moderate ligand field strength enables fast and highly reversible Zn deposition.

The first example of diazaphosphinine polycyclic aromatic hydrocarbons (DP-PAHs) is reported. The electronic structures and optoelectronic properties are highly tunable via the rich phosphorus chemistry. With balanced S₁ and T₁ emission, DP-PAH with P=S center exhibits a single-molecule white-light emitting character in the crystalline state.

A solid supramolecule based on a sulfobutylether-β-cyclodextrin and diarylethene derivative has been developed by a bromonaphthylpyridinium polymerization strategy. The supramolecule exhibits tunable phosphorescence emission in the amorphous state and can be applied for stimuli-responsive data encryption and anti-counterfeiting.

The selective formation of different macrocycles can be implemented using Cys residues within a peptide and chloroacetamides at the surface of a foldamer helix by placing the latter at precise locations. Helix rigidity and faster formation of smaller macrocycles make the favored product largely predictable.

In vivo fast-scan cyclic voltammetry was developed to measure behaviorally evoked dopamine release in the mushroom body of adult Drosophila melanogaster during sugar feeding. Sugar feeding stimulated robust dopamine release and its release was pharmacologically characterized. Dopamine release was increased after applying flupentixol and nisoxetine, demonstrating D2 receptors and dopamine transporters mediate sugar-evoked dopamine signaling.

A rapid and economical chemoselective labeling strategy was established involving a boronate ester reaction on a monolithic substrate. Only 15 minutes is required to complete the strategy and boron allows for recognition of labeled metabolites with no need for expensive additional isotopic encoding. The sensitivity was enhanced up to 1 600 times compared with non-labeled liquid chromatography–mass spectrometry methods.

The bi-polaron transport and magnetic field induced Pauli spin-blockade were revealed in redox-active molecules in molecular junctions (MJs), as evidenced by the magnetoresistance (MR) effect, which may bring new magnetic-electronic functionality to molecular scale electronic devices.

Herein, we report a dramatic enhancement in the reactivity of fullerenes (C₆₀/C₇₀)-tetrazine reaction inside a porous Zn-porphyrinic cage (Zn-PB) under sustainable conditions. Moreover, hydration-induced rearrangement of C60-LA inside Zn-PB facilitates its release from the Zn-PB cavity, thus enabling Zn-PB to catalyze fullerene-pyrazoline adduct formation without product inhibition.

Guided by intermolecular H-bonding and adsorption forces, an α-ketoester tumbles between two prochiral states in a chemisorbed diastereomeric complex.

The Lewis superacid bis(perchlorocatecholato)silane is applied in the selective catalytic C−O ring-closing metathesis of challenging oligo- and polyethers, enabling upcycling of polyethylene glycol. Based on detailed investigations of the reaction mechanism by DFT calculations, an improved second-generation silicon-based Lewis superacid is developed.

A novel dual-network structured hydrogel realizes stable and rechargeable solid-state zinc-air/iodide hybrid batteries.

An enantioselective synthesis of N−N bisindole atropisomers based on the de novo construction of one indole skeleton is presented. A wide variety of N−N axially chiral bisindoles were obtained in good yields with excellent enantioselectivities. Structurally diverse indole-pyrrole, indole-carbazole and non-biaryl-indole atropisomers possessing a chiral N−N axis were accessed using this protocol.

A combination of photoredox catalysis and energy transfer catalysis/direct photo-excitation enables cascade reactions of cyclopropanols and α-CF₃-olefins, in which two rings and three bonds are constructed in one reaction, affording fused gem-difluorooxetanes. The reaction shows broad substrate scope, complete cis-selectivity, and downstream transformations of the products demonstrated the synthetic potential.

We ideally design azobenzenes with alkyl chains (AZO(n)) as a photo trigger in the leuco dye based thermochromic system. The color developer in this system can be reversibly locked by Z-AZO(n), so that the leuco dye cannot capture the proton from the color developer to form the larger conjugate structure, while it can be released upon Z-to-E photoisomerization. This new strategy can be considered as a possible multi-input molecular logic system.

Tin heteroatoms on a silver catalyst generate very strong and atomically localized electric fields, as disclosed by differential phase contrast-scanning transmission electron microscopy (DPC-STEM). This results in a 100 % selectivity for CO at a wide range of potentials (−0.5 V to −1.1 V vs. RHE).

Disulfide bond formation is usually used in nature for the regulation and stabilization of protein conformations. This principle has now been expanded to control the conformational change of thiol-rich peptides into an amphiphilic β-hairpin conformation, which undergoes a subsequent self-assembly to form a mechanically rigid hydrogel. Such a stimuli-responsive feature allows the biomedical application of such peptides.

Boron-doped diamond catalyst is adopted for electrooxidation synthesis of formamide from methanol and ammonia with high activity and durability. A scale-up 8 L electrolyzer with an external renewable power supply for the production of formamide is designed to enable its scalable production (FE: 33.5 %, output: 36.9 g h⁻¹), which shows the potential for the large-scale electrosynthesis of formamide.