When a solution of [η5‑CpOs(CO)3]+[Al(OC(CF3)3)4]- is photolyzed in the presence of ethane, pentane or cyclopentane, photo-liberation of carbon monoxide occurs and the corresponding metal-alkane s‑complex, [η5‑CpOs(CO)2(alkane)]+ (where alkane = ethane, pentane and cyclopentane), forms. Here we report the NMR spectroscopic and computational investigations into the structure, reactivity, lifetimes and

Quaternary ammonium salts (QAS) are frequently utilized to modulate the structure of the cathodic electric double layer in processes such as water electrolysis and hydrogenation reactions. However, literature reports have shown that QAS can both suppress and promote hydrogen evolution activity, yet the underlying mechanisms remain incompletely understood. In this study, we experimentally observed that

The equilibrium dissociation constant (Kd) is a quantitative measure of the strength with which a drug binds to its receptor. Methods for determining Kd typically require a priori knowledge of protein concentration or mass. We report a simple dilution method for estimation of Kd using native mass spectrometry which can be applied to protein-ligand complexes involving proteins of unknown concentration

We present the synthesis and isolation of the first main-group phosphathioethynolates, [LBH2(SCP)] (L = SIMes, CAACMe; SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene, CAACMe = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene), in which phosphathioethynolate coordination occurs exclusively through the sulfur atom, giving rise to a phosphaalkyne-type structural

Despite their unique physical properties and diverse applications in materials science, poor solubility of polycyclic aromatic hydrocarbons (PAHs) limits further fine-tuning and investigation of these systems. Herein, we report a sulfoniumization strategy to solubilize and functionalize a diverse range of PAHs in a one-step protocol by the use of a triethylene glycol ether-substituted diaryl sulfoxide

This perspective begins with the discovery of the Grignard reaction by a graduate student in the last years of the 19th century, before describing why it has remained largely unexplained for more than a century. From the summary of what has been achieved, focusing on the computational aspects, it is now clear that further studies of the chemistry of any chemical species that is highly sensitive to

The field of light-emitting two-dimensional co-assemblies (2DCAs) is extending rapidly. Nevertheless, multifluorescence tunable 2DCAs are relatively underdeveloped, because the exploration of novel assembly strategies and noncovalent interactions to realize desirable photophysical features is still elusive. Herein, we present the first implementation of an aromatic cation-π interaction induced emissive

Capturing the time evolution and predicting kinetic sequences of states of physicochemical systems present significant challenges due to the precision and computational effort required. In this study, we demonstrate that ` Generative Pre-trained Transformer (GPT)', an artificial intelligence model renowned for machine translation and natural language processing, can be effectively adapted to predict

Matched molecular series (MMS) are series of molecules that differ only by a single modification at a specific site. The synthesis of MMS is a desirable strategy in drug discovery campaigns. Small aliphatic motifs, notably methyl, mono-, di- and trifluoromethyl substituents (C1 units), are known to have profound effects on the physiochemical properties and/or potency of drug candidates. In this context

The CO2/CO electroreduction reaction (CO2RR/CORR) to liquid products presents an enticing pathway to store intermittent renewable electricity. However, the selectivity for desirable high-value C3 products, such as n-propanol, remains unsatisfactory in CO2RR/CORR. Here, we report that *CO enrichment and proton regulation cooperatively enhance C1-C2 coupling by increasing CO pressure and utilizing proton

Click chemistry is important for its simplicity and versatility, however, condensation-based click reactions are limited by the general requirement of high temperatures and catalysts. Here, we report accelerated click reactions using boronic acids in microdroplets under ambient conditions without catalyst. The reaction between 2-formyl phenylboronic acid (2-FPBA) and substituted amines leads to the

Organic-inorganic metal halides with tunable and state room-temperature phosphorescence (RTP) properties receive broad interests in advanced luminescent materials. Herein, 2-(methylamino)pyridine (MAP), 2-[(methylamino)methyl]pyridine (MAMP), and 2-(2-methylaminoethyl)pyridine (MAEP) were designed and hybridized with Zn2+ and Cl-/Br-, yielding 11 hybrid materials. MAP-based compounds, with a narrow

Ketene was identified as an intermediate in syngas-to-olefins (STO) conversion catalyzed by metal oxide-zeolite composites, which sparked the hot debate on its formation mechanism and catalytic roles. Here we employed large-scale atomic simulations using global neural network potentials to explore the STO reaction pathways, and microkinetic simulations to couple the reaction kinetics in ZnCrOx|SAPO-34

Treatment of 2-(pyrazol-1-yl)-6-fluoropyridine with one equiv of the appropriate 4-substituted 1H-pyrazole in the presence of sodium hydride gives moderate yields of 2-(pyrazol-1-yl)-6-(4-methylpyrazol-1-yl)pyridine (LMe), 2-(pyrazol-1-yl)-6-(4-fluoropyrazol-1-yl)pyridine (LF), 2-(pyrazol-1-yl)-6-(4-chloropyrazol-1-yl)pyridine (LCl) and 2-(pyrazol-1-yl)-6-(4-bromopyrazol-1-yl)pyridine (LBr). Single

The synthesis of functionalized tropones constitutes an underexplored chemical space, primarily due to the intrinsic structural properties of the aromatic nucleus. This predicament has impeded extensive investigation into their potential applications in organic and medicinal chemistry. Here, we report a mild and straightforward visible-light-mediated protocol for the α-site-selective C(sp2)–H alkylation

A broad spectrum of optical nanomaterials, including organic molecules, quantum dots, and metallic nanoparticles, have attracted great attention in fields such as biological imaging, data storage, solid-state lasers and solar energy conversion owing to their nonlinear optical properties facilitated by the two-photon absorption process. However, their nonlinear optical properties, particularly photon

Here we report an unprecedented O-trifluoromethylation of ketones using chloro(phenyl)trifluoromethyl-λ3-iodane (CPTFI). Our method provides a new strategy for the facile synthesis of various synthetically valuable alkenyl trifluoromethyl ethers, particularly those CF3O-substituted terminal alkenes and cyclic alkenes that have been elusive until now, from simple aromatic, aliphatic, and cyclic ketones

The unstable electrode/electrolyte interface with erratic zinc (Zn) deposition, severe dendritic growth and parasitic side reactions deteriorates the reversibility, tolerance and sustainability of aqueous Zn ion batteries (AZIBs). Herein, a imidazolium-based cellulosic poly(ionic liquid)s ([CellMim]+) additive with hydrogen bond/ion dual regulation mechanism for aqueous electrolyte was designed and

Heterogeneous molecular catalysts (HMCs) with cobalt (Co) active sites are potent for electrochemical oxygen evolution reaction (OER) in the energy conversion applications. Such catalysts are typically operative through the classical redox mediated mechanism, where dynamic equilibriums of Co2+/3+ and Co3+/4+ redox are present before and throughout the OER cycle. The generation of low-valent Co2+ sites

Chemical interactions driven by external electric fields (EFs) can serve as a catalytic force for molecular machines and linkers for smart materials. In this context, the EF-driven dative bond is demonstrated through the study of interactions between PH3 and curved carbon-based nanostructures. The P→C dative bonds emerge only in the presence of EFs, whereas the interactions in the absence of EFs lead

Advanced materials with tunable thermal expansion properties have garnered significant attention due to their potential applications in thermomechanical sensing and resistance to thermal stress. Here, switchable colossal anisotropic thermal expansion (ATE) behaviors are realized in a Hofmann-type framework [Fe(bpy-NH2){Au(CN)2}2]·iPrOH (Fe·iPrOH, bpy-NH2 = [4,4'-Bipyridin]-3-amine) through a three-in-one

The development and sharing of computational databases for metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have significantly accelerated the exploration and application of these materials. Recently, molecular materials have emerged as a notable subclass of porous materials, characterized by their crystallinity, modularity, and processability. Among these, macrocycles and cages

Reduction as well as oxidation of the cyclo-As8 complex [{Cp’’Ta}2(µ,η2:2:2:2:1:1-As8)] (A, Cp’’ = 1,3-tBu2C5H3) are demonstrated to afford controlled dimerisation to unprecedented As16 species. The dication [{Cp’’Ta}4(µ4,η2:2:2:2:2:2:2:2:1:1:1:1-As16)]2+ slowly disproportionates in solution, yielding the largest polyarsenide species in a molecular complex known to date.

The fabrication of metalloenzyme-mimetic artificial catalyst is a promising approach to achieve maximum catalytic efficiency, but the rational integration of sophisticatedly optimized primary catalytic sites (PCS) and secondary coordination spheres (SCS) for specific transformation poses a grand challenge. Here in this work, we reported the tailored engineering of Cu PCS and perfluoroalkyl SCS onto

A highly efficient enantioselective N-acylative desymmetrization of sulfonimidamides with chloroformates was reported using chiral 4-arylpyridine-N-oxide as the catalyst, affording N-acylative sulfonimidamides with sulfur(VI)-stereocenters in high yields and excellent enantioselectivities. Experiments and DFT calculations support an acyl transfer mechanism, and the nucleophilic substitution of sulfonimidamide

The first asymmetric total synthesis of penicifuranone A was accomplished in eight steps through an NHC-catalyzed umpolung strategy. Key features of the synthesis include an Al-Salen catalyzed asymmetric cyanosilylation to install the tertiary alcohol of gregatin A, and an NHC catalyzed Stetter-Aldol cascade reaction. The umpolung strategy of benzyl aldehyde fragment facilitated a convergent formal

Point defects dictate the properties of many functional materials. The standard approach to modelling the thermodynamics of defects relies on a static description, where the change in Gibbs free energy is approximated by the internal energy. This approach has a low computational cost, but ignores contributions from atomic vibrations and structural configurations that can be accessed at finite temperatures

Direct protein analysis from complex cellular samples is crucial for understanding cellular diversity and disease mechanisms. Here, we explored the potential of SiNx solid-state nanopores for single-molecule protein analysis from complex cellular samples. Using the LOV2 protein as model, we designed a nanopore electrophoretic driver protein and fused it with LOV2, thereby enhancing the capture efficiency

Amino acids and other small chiral molecules play key roles in biochemistry. However, in order to understand how these molecules behave in vivo, it is necessary to study them under aqueous-phase conditions. Photoelectron circular dichroism (PECD) has emerged as an extremely sensitive probe of chiral molecules, but its suitability for application to aqueous solutions had not yet been proven. Here, we

Bismuth-based materials show promise for aqueous energy storage systems due to their unique layered structures and high storage capacity. Some bismuth-based materials have been applied to storage Zn2+ or NH4+, indicating that one bismuth-based compound may be innovatively used in both zinc-ion and ammonium-ion batteries (ZIBs and AIBs). Herein, we successfully design a poly(3,4-ethylenedioxythiophene)

Prussian blue analogues (PBAs) are widely recognized as one of the most promising cathode materials for sodium-ion batteries (SIBs). However, many unqualified PBAs with unsatisfactory electrochemical performance are difficult to dispose of and pose a risk of environmental contamination. Additionally, the production process of layered oxides, another popular cathode material for SIBs, requires prolonged

The influence of electric fields (EFs) on chemical reactions has attracted significant interest due to their ability to modulate reaction rates, pathways, and selectivity. Although EFs have been experimentally demonstrated to facilitate various reactions, clearer evidence for their role in covalent condensation has remained limited. Herein, we provide experimental evidence of electric-field-induced

Sn-based halide perovskites are expected to solve the problems of shuttle effect and sluggish redox kinetics of lithium polysulfides (LiPSs) in lithium-sulfur batteries (LSBs) due to its high conductivity and electrocatalytic activity, but its intrinsic catalytic mechanism for LiPSs remains to be explored. Herein, halide perovskites of Cs2SnX6 (X = Cl, Br, I) with varying halide anions are purposefully

This study addresses azobenzene's structural compression and reactivity under hydrostatic high-pressure conditions. Synchrotron X-ray diffraction data of single crystals compressed with neon as the pressure-transmitting medium allowed the refinement of the crystal structure up to 28 GPa, at which the onset of the reaction was observed. Analysis of the pressure-dependent lattice parameters reveals a

Polymer-based soft materials constructed from defined molecular pores, such as metal-organic polyhedra (MOPs), promise to merge the outstanding and diverse mechanical properties of conventional nonporous polymers with atomically-precise molecular recognition capabilities. Thus far, soft MOP networks have been constructed primarily using rigid, labile coordination bonds or dynamic covalent bonds, providing

A novel approach to the synthesis of the 2-thiabicyclo[2.1.1]hexane scaffold has been described. The method utilizes two highly reactive species: bicycle[1.1.0]butanes (BCBs) and thioketones. Their high reactivity enabled the formation of the desired product to occur under ambient conditions, without the need for catalysts, additives or light irradiation. To the best of our knowledge, this is the first

Mixed-halide wide-bandgap (WBG) perovskites are widely used in constructing tandem photovoltaics, but their practical applications are challenged by a phenomenon called photo-induced halide segregation (PIHS), which is detrimental to stability of the devices. The origin of such PIHS is not fully understood yet, restricting their further advancement. Here, we report a serendipitous discovery that PIHS

Interface engineering fundamentally revolutionizes magnesium-based hydrogen storage systems by orchestrating atomic-scale interactions and mass transport pathways through precisely engineered structural architectures and chemical environments. This review presents a paradigm-shifting framework that transcends conventional surface modification approaches, establishing interface engineering as a cornerstone

Genetic incorporation of noncanonical amino acids (ncAAs) harbouring catalytic side chains into proteins allows the creation of enzymes able to catalyse reactions that have no equivalent in nature. Here, we present for the first time the use of the ncAA 3-aminotyrosine (aY) as catalytic residue in a designer enzyme for iminium activation catalysis. Incorporation of aY into protein scaffold LmrR gave

Nontrivial protein topology has potential to revolutionize protein engineering by enabling the manipulation of proteins’ stability and dynamics. However, the rarity of topological proteins in nature poses a challenge for their design, synthesis and application, primarily due to the limited number of available entangling motifs as synthetic templates. Discovering these motifs is particularly difficult

The site-selective C-H bond fluorination of complex natural products is one of the more sought-after transformations in organic and medicinal chemistry. In many radical-based fluorinations, however, a tempest of poor regio- and stereoselectivity, multiple additions of fluorine, and difficult separations of products conspire to make selective monofluorination appear out of reach. In our fluorination

Understanding the interactions between metal-based nanoparticles and biological systems in complex environments (e.g., the human body, soils, and marine settings) remains challenging, especially at the single-cell and nanoscale levels. Capturing the dynamics of these interactions, such as metal distribution, nanoparticle growth, or degradation, in their native state (in vivo) is particularly difficult

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

Light-based therapeutic and imaging modalities, which emerge in clinical applications, rely on molecular tools, such as photocleavable protecting groups and photoswitches, that respond to photonic stimulus and translate it into a biological effect. However, optimisation of their key parameters (activation wavelength, band separation, fatigue resistance and half-life) is necessary to enable application

A novel approach for the efficient cleavage of the amide bonds in tertiary amides is reported. Based on the selective radical abstraction of a benzylic hydrogen atom by a CuBr2/Selectfluor hybrid system followed by a selective cleavage of an N–C bond, an acyl fluoride intermediate is formed. This intermediate may then be derivatized in a one-pot fashion. The reaction proceeds under mild conditions

Peri-acenes have shown great potential for use as functional materials because of their open-shell singlet biradical character. However, only a limited number of peri-acene derivatives larger than peri-tetracene have been synthesized to date, presumably owing to the low stability of the target compounds in addition to the complicated synthesis scheme. Here, a very simple synthesis route for the tetrabenzo[a

A hydroxyalkylation of N-heteroaromatics with aldehydes was achieved using a binary hybrid catalyst system comprising an acridinium photoredox catalyst and a thiophosphoric acid organocatalyst. The reaction proceeded through the following sequence: 1) photoredox-catalyzed single-electron oxidation of a thiophosphoric acid catalyst to generate a thiyl radical, 2) cleavage of the formyl C‒H bond of the

As metalloproteins exemplify, the chemical and physical properties of metal centers depend not only on their first but also on their second coordination sphere. Installing arrays of functional groups around the first coordination sphere of synthetic metal complexes is thus highly desirable, but it remains a challenging objective. Here we introduce a novel approach to produce tailored second coordination

The endoplasmic reticulum (ER) is a very important organelle responsible for crucial biosynthetic, sensing, and signalling functions in eukaryotic cells. In this work, we established a strategy of ligand regulation to enhance the singlet oxygen generation capacity and subcellular organelle localization ability of a rhodamine-decorated iridium(III) complex by variation of the cyclometallating ligand

A new family of ten dinuclear Ru(II) complexes based on the bis[pyrrolyl Ru(II)] triad scaffold, where two Ru(bpy)2centers are separated by a variety of organic linkers, was prepared to evaluate the influence of the organic chromophore on the spectroscopic and in vitro photodynamic therapy (PDT) properties of the compounds. The bis[pyrrolyl Ru(II)] triads absorbed strongly throughout the visible region

Non-noble metal nanocrystals with well-defined shapes have been attracting increasingly more attention in the last decade as potential alternatives to noble metals, by virtue of their Earth abundance combined with intriguing physical and chemical properties relevant for both fundamental studies and technological applications. Nevertheless, their synthesis is still primitive when compared to noble metals

Currently, there is no effective antiviral drugs nor vaccine for coronavirus disease 2019 (COVID-19)caused by acute respiratory syndrome coronavirus 2 (SARS-CoV-2). Due to its high conservativeness andlow similarity with human genes, SARS-CoV-2 main protease (Mpro) is one of the most favorable drug targets.However, the current understanding of the molecular mechanism of Mpro inhibition is limited by

Despite the remarkable mechanical/optical/electrical properties, the inorganic particles and dynamic polymer assemblies encountered the difficulties in compatibility with structural order and complexity. Here, covalent organic frameworks (COFs) constructed through reversible coupling reactions were exploited as dynamic porous polymers to prepare the inorganic nanocrystal-polymer assemblies. Experiencing