Pure organic thermally activated delayed fluorescence (TADF) materials hold great promise for efficient organic light-emitting diodes (OLEDs), yet developing high-performing blue TADF materials that integrate short delayed lifetime with aggregation induced emission (AIE) property remains a significant challenge. In this study, we developed three highly-efficient blue TADF emitters (32clCBP, 32clCXT

Catalytic electrochemical asymmetric catalysis starting to emerg as a promising strategy for the synthesis of chiral compounds. Herein, we report an asymmetric electrochemical nickel-catalysed reductive conjugate addition of alkenyl bromides/aryl iodides to α,β-unsaturated ketones in an undivided cell, leading to the addition products with high yields and excellent enantioselectivities (up to 96% yield

Transition metal-catalyzed 1,3-acyloxy migration of propargylic esters represents one of the most straightforward routes to access allene intermediates, which could engage in various fascinating subsequent transformations. However, this process is often limited to propargylic esters with electron-donating group due to intrinsic electronic bias and the subsequent intermolecular reactions are quite limited

Boron-based frustrated Lewis pairs (FLPs) have become well-established catalysts for the hydrogenation of a wide range of functional groups. Conversely, aluminium-based FLP hydrogenation catalysts are less common, especially for CO2 reduction. They are mostly confined to the hydrogenation of imines, alkenes, and alkynes even though aluminium is much more abundant than boron and forms structurally related

Scintillation-based X-ray detection has been widely used in various fields from medical diagnostics to security. In this study, we report four new CuI–based hybrid materials consisting of anionic inorganic chains coordinated to cationic ligands. Due to their unique bonding nature, these compounds demonstrate high stability, solution-processability, and efficient photoluminescence with PLQYs reaching

Stable planar dithienoarsinines were synthesized and structurally characterized. These compounds exhibit monomeric structures in the solution and solid states, avoiding dimerization, even in the absence of steric protection. They exhibited high global aromaticity with 14 or 22π-electron systems. In the solid state, intermolecular interactions through arsenic atoms were observed, and As···As interactions

In nonpolar solvents, alkyllithium-initiated 1,3-butadiene polymerization exhibits high 1,4-selectivity, which shifts towards 1,2-selectivity upon the addition of Lewis bases. For the past 50 years, the prevailing hypothesis has suggested that Lewis bases primarily influence regioselectivity through electronic effects. However, our study reveals that steric hindrance also plays a crucial role. Using

Aberrant microRNA (miRNA) expression is associated with various types of carcinogenesis, making miRNA a promising candidate for diagnostic and therapeutic biomarkers. However, in situ miRNA diagnostics remains a significant challenge owing to the various biological barriers. Herein, we report a novel miRNA imaging probe consisting of a PEG-Polylysine-PNIPAM polymer matrix-modified small Fe3O4 nanoparticle

Molecular photoswitches have been incorporated into polymer backbones to control the macromolecular conformations by structural changes of the main-chain photoswitches. However, previous photoswitches installed in the main chains are thermolabile, which precludes deep understanding, precise regulation, and practical applications of the macromolecular conformational changes. Herein, we focus on sterically

Zirconium-based porous coordination cages have been widely studied and have shown to be potentially useful for many applications as a result of their tunability and stability, likely as a result of their status as a molecular equivalent to the small 8 Å tetrahedral pores of UiO-66 (Zr6(μ3-O)4(μ2-OH)4(C8O4H4)6). Functional groups attached to these molecular materials endows them with a range of tunable

Recent studies have revealed critical roles for the local environments surrounding metallocofactors, such as the newly identified CuD site in particulate methane monooxygenases (pMMOs) and the second sphere aromatic residues in lytic polysaccharide monooxygenases (LPMOs), implicated in the protection against oxidative damage. However, these features are subjects of continued debate. Our work utilizes

We are grateful to the reviewers for their globally positive evaluation and the very constructive criticism and suggestions they made. In particular, we acknowledge their request for a detailed discussion of the lessons the community can learn in view of devising new and better performing fluorescent mutants of AR-3. We have now addressed this question in a new section entitled "Engineering Aspects"

Water microdroplets containing 100 µM HAuCl4 have been shown to reduce gold ions into gold nanoparticles spontaneously. It has been suggested that this chemical transformation takes place at the air–water interface of microdroplets, albeit without mechanistic insights. We compared the fate of several metallic salts in water, methanol, ethanol, and acetonitrile in bulk phase and microdroplet geometry

Constructing highly efficient electrocatalysts via interface manipulation and structural design to facilitate rapid electron transfer in electrocatalytic nitrate-to-ammonia conversion is crucial to attaining superior NH3 yield rate. Here, a Mott-Schottky type electrocatalyst of Co/In2O3 with a continuous fiber structure has been designed to boost the electrocatalytic nitrate-to-ammonia performance

The cationic molybdenum pentahydride complex [MoH5(depe)2]+ (depe = 1,2-bis(diethylphosphino)ethane) is shown to undergo two consecutive reactions with carbon dioxide. In the initial, room-temperature process, classical insertion of CO2 into a metal−hydride bond is observed, resulting in the formation of the expected formate complex, [MoH2(HCOO)(depe)2]+. Further reactivity is triggered at temperature

Despite their promising potential, e.g., as ditopic, cooperatively binding Lewis acids, 9,10-dihydro-9,10-dialuminaanthracenes (DAA-R2; R: terminal Al-bonded substituent) have remained unexplored for long due to the challenges in synthesizing the ligand-free species. We demonstrate that DAA-Me2 is accessible via the reaction of 1,2-(Me3Sn)2C6H4 with AlMe3, producing volatile SnMe4 as the sole byproduct

The field of natural language processing (NLP) has witnessed a transformative shift with the emergence of large language models (LLMs), revolutionizing various language tasks and applications, and the integration of LLM into specialized domains enhances their capabilities for domain-specific applications. Notably, NLP has made significant strides in organic chemistry, particularly in predicting synthetic

The efficient realization of closed-loop process is an ultimate goal for reusing the retired lithium-ion batteries (LIBs), yet the complicated recycling processes of leaching and purification in acid atmosphere are totally different with the regeneration method of cathode precursor in alkali solution inevitably resulting in the redundant consumption of acid/ammonia solutions and increased burden of

Copper homeostasis is crucial for cells, especially for rapidly proliferating cancerous cells. Copper imbalance-induced cell death (i.e., cuproptosis) has emerged as a new strategy for tumor therapy. While copper accumulation-induced cuproptosis has been extensively investigated and its underlying mechanism recently elaborated, copper depletion-induced cuproptosis remains largely unexplored. Herein

Nakano et al. reported that the antiaromatic indenofluorene (IF) isomers are diradicaloid molecules having varying degrees of open-shell character, with indeno[1,2-b]fluorene displaying a weaker diradical character index (y0 = 0.072). Unlike 6,12-trimethylsilylethynyl disubstituted [1,2-b]IF, the 6,12-aryl disubstituted [1,2-b]IF derivatives did not show any experimental evidence of diradical properties

The naturally sluggish redox kinetics and limited utilization associated with the sulfur conversion in Zn/S electrochemistry hinder its real application. Herein, we report an in-situ phase reconstruction strategy that activates the catalysis activity of vanadium oxides for invoking the redox-catalysis to manipulate reversible sulfur conversion. It was identified that the V2O3@C/S precursor derived

For sodium-ion batteries, solving the pain point of short cycle life is the key to large-scale promotion for the industry, and the electrolyte plays an important role on it. Herein, this work is on purpose to design a practical sodium ion battery electrolyte with industrial application value and introduces anhydride compounds as additives for the first time. Meanwhile, by adjusting the solvent composition

RAS proteins are the most frequently mutated in cancer, yet they have proved extremely difficult to target for drug discovery, largely because interfering with the interaction of RAS with its downstream effectors comes up against the challenge of protein-protein interactions (PPIs). Sequence-defined synthetic oligomers could combine the precision and customisability of synthetic molecules with the

The Small Ubiquitin-like Modifier (SUMO) is a crucial post-translational modifier of proteins, playing a key role in various cellular functions. All SUMOs are synthesized as precursor proteins that must be proteolytically processed. However, the maturation process of cleaving the extending C-terminal tail, preceding SUMOylation of substrates, remains poorly understood, especially within cellular environments

Mechanistic studies of thiol reactivity can be challenging because electrophilic reaction intermediates, such as sulfenic acids (RSOH) and sulfenyl chlorides (RSCl), are generally too reactive to be observed directly. Herein we report the design and synthesis of a sterically-encumbered fluorinated triptycene thiol to enable direct observation of reaction intermediates in aqueous buffer by 19F NMR,

Meroterpenoids are hybrid natural products that arise from the integration of terpenoid and non-terpenoid biosynthetic pathways. While the biosynthesis of fungal meroterpenoids typically follows a well-established sequence of prenylation, epoxidation, and cyclization, the pathways for bacterial perhydrophenanthrene meroterpenoids remain poorly understood. In this study, we report the construction of

Responsive nanomaterials have emerged as promising candidates for advanced drug delivery systems (DDSs), offering the potential to precisely target disease sites and enhance treatment efficacy. To fulfil their potential, such materials need to be engineered to respond to specific variations in biological conditions. In this work, we present a series of pH/redox dual-responsive hybrid nanoparticles

Electrocatalytic water splitting in alkaline media plays an important role in hydrogen production technology. Normally, the catalytic activity of commonly used transition metal oxides usually suffers from unsatisfactory electron conductivity and unfavorable binding strength for transition intermediates. To boost the intrinsic catalytic activity, we propose a rational strategy to construct lattice distorted

The first carbocyclic gallylene [(ADC)2Ga(GaI2)] and bis-gallylene [(ADC)Ga]2 (ADC = PhC{N(Dipp)C}2; Dipp = 2,6-iPr2C6H3) featuring a central C4Ga2 ring annulated between two 1,3-imidazole rings are prepared by KC8 reductions of [(ADC)GaI2]2. Treatment of [(ADC)Ga]2 with Fe2(CO)9 affords complex [(ADC)GaFe(CO)4]2 in which each Ga(I) atom serves as a two-electron donor. [(ADC)Ga]2 activates white phosphorus

Developing single crystals of covalent organic polymers (COPs) is highly attractive as they can afford precise structural information for studying internal interactions. Employing dative boron-nitrogen (B-N) bonds to construct single-crystalline COPs is feasible since the dynamic linkages can self-correct errors, thus improving crystallization. In this project, we develop single crystals of a new COP

Bis(methylene)-λ5-phosphane anions, i.e., anionic phosphorus-centered heteroallene-type molecules, were obtained from the desilylation of a bis(silyl)methyl-substituted phosphaalkene. Their molecular structures, which were determined using spectroscopic techniques and single-crystal X-ray diffraction analysis, suggest that the central di-coordinated P atom is engaged in cumulative C=P=C π-bonds with

A photo-promoted oxidative cyclization, that is, Mallory reaction of 2,3-diarylbenzophopholes has been developed. With an assistance of Bi(OTf)3 Lewis acid, the reaction proceeds smoothly under visible light irradiation even without any external oxidants. The newly developed dehydrogenative conditions are compatible with various functional groups and substitution patterns, which enables the streamlined

Abstract: Photoacid generators (PAGs) and photohydride generators (PHGs) are specific photolabile protecting groups that release acid and hydride, respectively. Over the past decade, great efforts have been devoted to developing novel PAGs and PHGs with advanced efficiency, and among which, one of the promising candidates is the diarylethylene (DAE)-based PAGs and PHGs, which release acids/hydrides

Superconductivity can be considered among the most exciting discoveries in material science of the XXth century. However, the hard conditions for the synthesis and the difficult characterization, make the statement of new high critical temperature (Tc) complex from the experimental viewpoint and have recently led to several hot controversies in the literature. In this panorama, theory has become a

Cyclopropanes, valuable C3 building blocks in organic synthesis, possess high strain energy and inherent stability. We present an efficient, environmentally benign 1,3-oxyheteroarylation of aryl cyclopropanes using azine N-oxides as bifunctional reagents under visible light irradiation. This metal-free method yields β-pyridyl ketones under mild conditions. Mechanistic studies reveal a photo-induced

Stimuli-responsive switchable molecules represent an important category of magnetic materials with significant potential for functional devices. However, engineering complexes with controlled switchability remains challenging due to their sensitivity to lattice interactions. Herein, we report a [Fe2Co2] square complex [FeTp(CN)3]2[Co{(F5-Ph)Py}2]2•2ClO4•4CH3OH•2H2O {1•4CH3OH•2H2O; (F5-Ph)Py = (Z)-

Poly(L-lactic acid) (PLLA) is commercially successful bio-based plastic, where end-of-life materials can undergo industrial composting. To create a circular economy, a desirable alternative to composting is chemical recycling to monomer (CRM), where direct depolymerisation to L-lactide can be achieved. CRM of PLLA is typically impeded by thermal decomposition and side reactions, due to the high ceiling

Alzheimer’s Disease (AD) is a neurodegenerative disorder proven to be caused by the aggregation of protein tau into fibrils, resulting in neuronal death. The irreparable neuronal damage leads to irreversible symptoms with no cure; therefore, disaggregation of these tau fibrils could be targeted as a therapeutic approach to AD. Here we have developed a fungal natural product library to screen for secondary

Using a diverse array of thermally robust phosphine enediyne ligands (dxpeb, X = Ph, Ph-pOCH3, Ph-pCF3, Ph-m2CH3, Ph-m2CF3, iPr, Cy, and tBu) a novel suite of cisplatin-like Pt(II) metalloenediynes (3, Pt(dxpeb)Cl2) has been synthesized and represents unique electronic perturbations on thermal Bergman cyclization kinetics. Complexes 3e (Ph-m2CF3) and 3f (iPr) are the first of this structure type to

Porphyrin derivatives serve as photocatalysts in reversible-deactivation radical polymerization and as photosensitizers in photodynamic therapy (PDT). Herein, a triple function porphyrin, ZnTPPC6Br, was synthesized as photocatalyst and initiator for photoATRP. Oxygen-tolerant photoATRP produced fructose-based star-shaped glycopolymers as targeted photosensitizers for PDT. ZnTPPC6Br/CuII/PMDETA could

Conjugated ladder polymers (CLPs) are difficult yet captivating synthetic targets due to their fully unsaturated fused backbones. Inherent challenges associated with their synthesis often lead to low yields, structural defects, and insoluble products. Here a new method to form CLPs is demonstrated, utilizing a high-yielding dimerization of annulated zirconacyclopentadienes to form cyclooctatetraene

The catalytic asymmetric hydrogenation of ketones reflect an important way to prepare valuable chiral alcohols. Understanding how transition metals promote these reactions is key to the rational design of more active, selective and sustainable catalysts. A highly unusual mechanism for the asymmetric hydrogenation of benzophenone, catalysed by an anionic IrIII hydride system with a strong counterion

Metal-Organic Frameworks (MOFs) constructed using cross-linked oligomeric or polymeric ligands (OligoMOFs and PolyMOFs respectively) have so far relied on a handful of canonical structural blueprints, in which the cross-links have not played a significant role in determining structure. In this study, we show that cross-links between terephthalate ligands in dabco-based Zn-MOFs (DMOFs) can exert control

Cleavage of lignin ether bonds via transfer hydrogenolysis is a promising route to valorize lignin, but processes that use mild reaction conditions and exploit renewable hydrogen donor solvents (rather than molecular hydrogen) are economically advantageous. Herein we demonstrate the efficient catalytic transfer hydrogenolysis and tandem decarbonylation of lignin model compounds possessing aromatic

The stability of metal-organic frameworks (MOFs) in the presence of water is crucial for a wide range of applications, including the production of freshwater, desiccation, humidity control, heat pumps/chillers and capture and separation of gas. In particular, their stability under steam flow is essential since most industrial streams contain water vapor. Nevertheless, to the best of our knowledge,

In biological systems, nitric oxide (NO) is a crucial signaling molecule that regulates a wide range of physiological and pathological processes. Given the significance of NO, there has been considerable interest in delivering NO exogenously, particularly through light as a non-invasive therapeutic approach. However, due to the high reactivity and instability of NO under physiological conditions, directly

The accurate modeling of dissociative chemisorption of molecules on metal surfaces presents an exciting scientific challenge to theorists, and is practically relevant to modeling heterogeneously catalyzed reactive processes in computational catalysis. The first important scientific challenge in the field is that accurate barriers for dissociative chemisorption are not yet available from first principles

Peptide stapling reactions represent powerful methods for structuring native α-helices to improve their bioactivity in targeting protein-protein inetractions (PPIs). In light of a growing need for regio- and positionally selective stapling methods involving natural amino acid residues in their unprotected states, we report a rapid, mild, and highly chemoselective three-component stapling reation using

Anion recognition in water by synthetic host molecules has been a hot and challenging topic. It has been considered difficult because the water molecules compete for the recognition units. In this study, we have successfully created a novel macrocycle that achieves precise recognition through multipoint hydrogen bonding in harmony with the water molecules. Specifically, an N-methylpyridinium amide

Understanding the structure-chiroptical activity relationship in chiral perovskites is of great significance as it provides a pathway to control light-matter interactions. Although many reports have shown various chiral structures with distinctive chiroptical responses, a clear structure-property relationship is still missing, partially stemming from the poor understanding of the optical activity mechanism

Metal halide perovskites (MHPs) have been developed rapidly in light-emitting diodes (LEDs), laser, solar cells, photodetectors and other fields in recent years due to their excellent photoelectronic properties, which attract more researchers’ attention. Perovskite LEDs show great promise in the next generation of lighting and display technologies, and external quantum efficiency (EQE) values of polycrystalline

Transition metal-catalyzed carbocyclization reactions offer a powerful method for the stereoselective assembly of complex, highly substituted (poly)cyclic scaffolds. Although 1,6-enynes are common substrates for these transformations, using polysubstituted alkene derivatives to construct functionalized cyclic products remains challenging due to significantly lower reactivity. This Perspective highlights

The performance of a photoinitiator is key to control efficiency and resolution in 3D laser nanoprinting. Upon light absorption, a cascade of competing photophysical processes leads to photochemical reactions toward radical formation that initiates free radical polymerization (FRP). Here, we investigate 7-diethylamino-3-thenoylcoumarin (DETC), belonging to efficient and frequently used photoinitiators

Rechargeable aluminum-ion batteries have attracted increasing attention owing to the advantageous multivalent ion storage mechanism thus high theoretical capacity as well as inherent safety and low cost of using aluminum. However, their development has been largely impeded by the lack of suitable positive electrodes to provide both sufficient energy density and satisfactory rate capability. Here we

Zinc-ion batteries (ZIBs) have received much research and attention due to their advantages of safety, non-toxicity, simple manufacture, and element abundance. Nevertheless, serious problems still remain for their anodes, with dendrite development, corrosion, passivation, and the parasitic hydrogen evolution reaction due to their unique aqueous electrolyte system constituting the main issues that must

The rates of liquid-phase, acid-catalyzed reactions relevant to the upgrading of biomass into high-value chemicals are highly sensitive to solvent composition and identifying suitable solvent mixtures is theoretically and experimentally challenging. We show that the complex atomistic configurations of reactant-solvent environments generated by classical molecular dynamics simulations can be exploited

We report here cobalt−N-heterocyclic carbene catalytic systems for the intramolecular decarbonylative coupling through the chelation-assisted C−C bond cleavage of acylindoles and diarylketones. The reaction tolerates a wide range of functional groups such as alkyl, aryl, and heteroaryl groups, giving the decarbonylative products in moderate to excellent yields. This transformation involves the cleavage

We present herein an unconventional tandem [3,3]-sigmatropic rearrangement/[2+2] cycloaddition of simple dipropargylphosphonates to deliver a range of bicyclic polysubstituted cyclobutenes and cyclobutanes under Ag/Co relay catalysis. An interesting switch from allene-allene to allene-alkyne cycloaddition was observed based on the substitution of the substrates, which further diversified the range

The deprotonation of propargylic C–H bonds for subsequent functionalization typically requires stoichiometric metal alkyl or amide reagents. In addition to the undesirable generation of stoichiometric metallic waste, these conditions limit the functional group compatibility and versatility of this functionalization strategy and often result in regioisomeric mixtures. In this Article, we report the