Combining magnetic materials with high dielectric MXene has been proven to be an effective method to construct superb electromagnetic protective materials as they can introduce interface polarization and collaborate dielectric-magnetic loss mechanism. However, the application of such hybrid structure is constrained by the obvious instability of MXene at acidic, basic, and high-temperature environments. Herein, inspired by the great advantage of unique “hard shell and soft core” protective structure of natural coconuts, polydopamine (PDA)@Co₃O₄/Ti₃C₂T_x (M)/polytetrafluoroethylene (PTFE) composite was fabricated for durable electromagnetic protective application. In this structure, the antioxidant PDA and chemically inert PTFE serve as a robust protective layer analogous to a “coconut shell”, effectively encapsulating the Co₃O₄/Ti₃C₂T_x core, which functions as the primary additive for electromagnetic wave attenuation. The PDA@Co₃O₄/M/PTFE composite demonstrates a reflection loss (RL) value of −59.12 dB and an effective absorption bandwidth (EAB) of 6.72 GHz. It also exhibits electromagnetic shielding effectiveness of up to 27.67 dB and an absorption efficiency of 94.12%. Furthermore, the composite shows excellent environmental stability under acidic, basic, and sunlight exposure conditions, along with outstanding hydrophobic and flame-retardant properties. In conclusion, the PDA@Co₃O₄/M/PTFE has significant potential to satisfy electromagnetic protective need of electronic systems, aerospace, and defense industries under harsh conditions.

Extreme ultraviolet (EUV) lithography is a key technology for sub-7 nm nodes semiconductor manufacturing but faces challenges due to low energy conversion efficiency and weak sensitivity of photoresists. Antimony (Sb)-based materials have attracted increasing attention for their high EUV absorption cross-section. Herein, through a fluorine modification strategy, we functionalized a Sb₂-oxo cluster with tailored carboxylic acid ligands to achieve dual-tone photoresist control. Crucially, fluorinated ligands induced positive- tone patterning with enhanced sensitivity, while the non-fluorinated ligand decorated Sb₂-oxo cluster maintained conventional negative-tone behavior. Combined X-ray photoelectron spectroscopy (XPS) analysis, UV-vis absorption spectroscopy analysis, and theoretical calculations highlight the potential of fluorine to alter the inherent cross-linking mechanisms. This work not only enriches the examples of metal oxo cluster based positive photoresists but also provides an effective approach to manipulating photoresist polarity at the molecular level.

The construction of chiral tetraarylmethanes has emerged as a rapidly developing field in organic synthesis. In previously developed strategies, the chiral tetraarylmethanes molecules were primarily based on quinone methides or 2-methyleneindoles type scaffolds, wherein the interaction between alkoxy-type "tag group" and chiral phosphoric acid played a crucial role in distinguishing between two sterically similar aryl substituents during the enantioselective nucleophilic addition step. In this work, we achieved the first synthesis of chiral tetraarylmethanes based on 7-indole imine methides, in which the methylthio "type tag" group is pivotal for achieving effective chiral recognition, rather than the conventional alkoxy group. Furthermore, subsequent derivatization of the chiral products and their evaluation in anti-cancer assays underscore the synthetic and biological significance of these structurally unique 7-indole containing tetraarylmethane derivatives.

Although rotaxane dendrimers have shown extensive applications in stimuli-responsive materials, photocatalysis, and chiral luminescent materials, the detailed elucidation of their stimuli-induced motion behaviors remains a major challenge primarily attributed to the dynamic and complicated three-dimensional architectures. Herein, we present the first successful preparation of a new family of selectively-deuterated rotaxane dendrimers, in which deuterated pillar[5]arene wheels were precisely distributed on different generations of the dendrimer skeleton. In particular, the third-generation fully-deuterated rotaxane dendrimer with 28 deuterated [2]rotaxane units was successfully synthesized, enabling the deuteration of 1,400 hydrogen atoms. More importantly, the introduction of acetate anions at varying ratios induced differential contraction motions across different generations of the rotaxane dendrimer, as systematically investigated using a combination of ¹H NMR and small-angle neutron scattering (SANS) techniques, providing fundamental insights into the operational mechanism of molecular machines and the cooperative behavior of dynamic systems for further development of novel smart nanodevices and materials.

Circularly polarized luminescence (CPL) materials are attracting considerable attention due to their unique chiroptical properties and great potential in information encryption and smart sensing. However, arbitrary patterning of multicolor CPL materials with giant dissymmetry factor (g_lum > 1.5) in a scalable and customized way still remains challenging. Inspired by the cuticle of beetles, we present a general strategy for the fabrication of robust CPL films via twist-stacking (TS) assembly of highly oriented polyfluorene (PF) films. We demonstrate strong CPL amplification via the continuous TS assembly of highly oriented PF films or the heterogeneous assembly with anisotropic poly(vinyl alcohol) (PVA) layer. Moreover, by mutually perpendicular stacking of two heterogeneous PF/PVA TS patterns, dual-sided Janus displays, generating dynamic switchable CPL patterns on opposing surfaces, could be achieved. These hybrid films exclusively display decipherable information and tailorable CPL patterns under UV irradiation in darkness, while concealing all data in daylight. Thus, a multimodal information encryption system based on these biomimetic multicolored hybrid films can be devised through the programmed decryption process.

Elucidating the structure–property–activity relationship in fluorinated COFs is crucial for advancing the rational design of high-performance COF-based photocatalysts. Despite its significance in guiding the development of next-generation fluorinated COF photocatalysts, the interplay between the quantity, spatial distribution, and integration sites of functional groups within the COF's backbone at the molecular level remains underexplored. To address this, we propose a controlled fluorination molecular engineering strategy to systematically elucidate this relationship. By precisely tuning the number and positional arrangement of fluorine atoms, we effectively enhance carrier dynamics and interfacial reaction kinetics, thereby driving efficient photocatalytic hydrogen evolution reaction. Notably, the optimized TP-COF-F-3 exhibited an apparent quantum yield of 4.09% at 500 nm, outperforming most reported COF-based photocatalysts. These findings underscore a transformative approach to the molecular design of COF photocatalysts, providing insights for the development of advanced and sustainable photocatalytic systems.

The selective functionalization of unactivated benzylic C–H bonds in arenes and N-heteroarenes remains a pivotal challenge in synthetic chemistry, particularly for constructing oxygen-containing functional groups with precision. Herein, we present an efficient photoredox-catalysis strategy for the selective oxidation of benzylic C(sp³)–H bonds in both aromatic and N-heteroaromatic systems. This protocol employed cyclic hypervalent iodine reagents as a bifunctional platform functioning as hydrogen atom transfer (HAT) agent or radical precursor to facilitate the dual oxidative radical–polar crossover (ORPC) process under mild conditions, wherein water served as either a nucleophilic oxygen donor or quenching agent to initiate the oxidation process.

Multifunctionalization reactions involving reactive intermediates offer powerful strategies for the rapid construction of complex molecules. Herein, we describe two trifunctionalization reactions of pyrazoleamide-derived metal carbenes. Both transformations are proposed to proceed through a zwitterionic intermediate, formed via nucleophilic attack and pyrazole migration, followed by electrophilic trapping. This approach enables the efficient synthesis of 3-hydroxy-2-oxindole derivatives from isatins and amines in good yields, as well as chiral β-aminoamide derivatives via a Rh/CPA co-catalytic system with excellent enantioselectivity. Importantly, both classes of compounds exhibited significant inhibitory activity against multiple tumor cell lines.

Developing persistent room temperature phosphorescence (RTP) materials with ultra-bright afterglow has been a great challenge. Most organic RTP systems emitted dim afterglow, which is only visible in dark environments. Herein, we reported a robust ultra-high afterglow brightness system by doping a type of phenyl(triphenylen-2-yl)methanone (TpP) derivatives into a non-polar polymeric matrix, styrene-ethylene butylene-styrene (SEBS). The strong π-π interaction between TpP emitters and SEBS, combined with their suitable energy levels, ensured that the doped materials exhibited persistent phosphorescence with an extraordinarily bright afterglow, reaching values up to 6.0 cd/m². Such a high afterglow was just slightly reduced to 2.3 cd/m², even at a high temperature of 353 K. Their afterglow can even be clearly observed under sunlight. Further comparative studies revealed that the phenyl carbonyl unit in these TpP-type compounds is also a crucial factor, significantly enhancing the efficiency of the intersystem crossing. Additionally, the bright afterglow demonstrated excellent resistance to UV light and oxygen, ascribed to the inherent properties of the SEBS matrix itself. Therefore, this work provides an effective design strategy for the preparation of organic afterglow materials with high brightness and persistent emission.

The chiral 2,3-dihydrobenzofuran (DHB) scaffold is a privileged motif in bioactive natural products and preclinical therapeutic candidates, yet practical enantioselective syntheses remain scarce. We report a chiral Rh/Hf/(S)-DTBM-SEGPHOS bimetallic catalytic system enabling asymmetric hydrogenation of benzofurans with hydrogen source, delivering diverse DHBs (37 examples) in excellent yields (up to 98%) and enantioselectivities (up to 99% ee). Gram-scale synthesis and deuterium labeling with D₂O (8 examples) validate the method's scalability and utility in biological studies and drug design.

We report a practical, light-driven nickel-catalyzed hydrocyanation of alkenes using readily available isonitriles as cyanide surrogates. This method proceeds under mild conditions, tolerates a wide range of functional groups, and delivers linear alkyl nitriles with high efficiency and excellent regioselectivity. The protocol is broadly applicable, including to the late-stage functionalization of complex, bioactive molecules derived from natural products and pharmaceuticals, providing a direct route to valuable nitrile-containing building blocks and facilitating rapid access to drug-like scaffolds.

Chiral bipyridines represent a class of ligands noted for their distinctive reactivity and stereoselectivity in metal-catalyzed reactions. Herein, we have developed a new class of bifunctional C₂-symmetric chiral bipyridine-type tetradentate ligands, abbreviated as Bpy-Bisulidines. These crab-shape ligands feature that: (1) bipyridine framework possesses the rich coordination ability with various metal ions; (2) chiral imidazolidine could generate a deep chiral pocket; (3) C₂-symmetry could reduce the number of possible transition states; (4) rigid chiral enviroments are close to the metal, and (5) imidazolidine N-H moiety acts as hydrogen-bonding donor. The newly developed chiral Bpy-Bisulidine ligands were successfully applied in Ni(II)-catalyzed asymmetric Friedel-Crafts alkylation reaction and inverse-electron-demand Hetero-Diels-Alder reactions, achieving excellent stereoselectivities. Our work is the first example of bifunctional C₂-symmetric chiral imidazolidine-type tetradentate ligands. X-ray crystallographic analysis of the Bpy-Bisulidine-Ni(OTf)₂ complex, control experiments and linear correlation showed that the catalytically active species was a monomeric catalyst.

The direct construction of C(sp³)−C(sp²) bonds from operationally convenient, synthetically versatile, and readily accessible building blocks serves as a key driving force for innovation in synthetic organic chemistry. These scaffolds enhance drug properties, facilitating the development and clinical translation of lead compounds. In this work, we report the first use of the synergistic effect between Co and Ce LMCT catalysis, presenting an effective photocatalytic strategy for the decarboxylative Heck type coupling reaction of primary, secondary, and tertiary aliphatic carboxylic acids. Under mild conditions, this method achieves the effective coupling of C(sp³) and C(sp²) motifs, demonstrating excellent functional group tolerance and offering significant potential for the late-stage modification of bioactive carboxylic acids. Notably, this transformation proceeds without the need for external oxidants or pre functionalization of the carboxylic acids, with H₂ and CO₂ as the sole byproducts.

Cu-BTC (BTC = 1,3,5-benzenetricarboxylic acid) framework faces environmental and scalability challenges in conventional synthesis due to energy-intensive processes, using toxic solvents and costly precursors, with nanoparticle integration further complicating production through multi-step procedures that degrade structural integrity. This study developed an innovative ambient-temperature synthesis of Cu-N coordinated Cu-BTC MOF containing dispersed Cu/Cu₂O nanoparticles using economical Cu⁰ powder. The N-ligand-mediated oxidation and deprotonation simultaneously achieve: (1) incorporation of 5 nm nanoparticles, (2) in situ formation of catalytic Cu–N bonds, and (3) manifestation of multifunctional catalytic performance. The Cu/Cu₂O@Cu-BTC/N composite demonstrates outstanding catalytic activity, achieving high yields across multiple reactions: 91% in Knoevenagel condensation, 89% in Sonogashira coupling, 99% in Ullmann-type C–N coupling, and 97% in indole C2-acylation, along with exceptional photocatalytic hydrogen evolution performance (7.06 mmol·g^–1·h^–1). Notably, the synthetic protocol demonstrates excellent scalability, maintaining 90% yield at both 1 g and 10 g scales, thereby establishing a sustainable pathway for large-scale production of multifunctional MOF catalysts with promising applications in green chemistry and energy-related fields.

Phosphine oxides featuring P-stereogenic center are popularly used in chiral ligands, catalysts and materials. Related methods focus on the preparation of P(V) skeleton containing different types of carbon substituents for facile enantiocontrol. In comparison, phosphine oxide containing all three C(sp²)-substituents is seldom studied. Here we describe a novel protocol to achieve fully C(sp²)-substituted P(V) stereocenters via synergistic Pd/Co-catalyzed hydrophosphinylation of conjugated enynes with masked P(V) nucleophile. 1,2-Hydrophosphinylation is exclusively observed, different from prior work involving 1,4-hydrophosphinylation. A group of newly modified chiral Boxmi ligands guarantee the high stereocontrol of the transformation. Mechanistic studies suggest the outer-sphere allylic substitution as the rate-determining step.

Herein, we report the synthesis of multifunctionalized trans- and cis-cyclobutane-based γ-aminobutyric acid derivatives via diastereodivergent Cu(OTf)₂-catalyzed strain-release reactions of bicyclo[1.1.0]butanes with amines. This protocol enables precise control of product configuration via ligand selection, providing a powerful tool for modulating the stereochemistry of the resulting compounds. In addition, the synthesized cyclobutane-based γ-aminobutyric acid derivatives significantly expand substituent diversity, thereby greatly enhancing molecular complexity. The method proceeds under mild conditions and exhibits excellent tolerance toward a broad range of functional groups, making it a versatile platform for the development of novel drug candidates.

A novel asymmetric [4+2] cycloaddition of indolylmethanols with aurones via chiral phosphoric acid (CPA) catalysis has been established. Enantioenriched indole-fused spiro compounds were obtained in good yields (60%–89%) with excellent diastereoselectivities (up to >19 : 1 dr) and enantioselectivities (83%–99% ee) with broad substrate scope. This approach not only enabled the first catalytic asymmetric [4+2] cycloaddition of 3-methyl-2-indolylmethanols, but also represented different reactivity from traditional indolylmethanol chemistry. In this reaction, 3-methyl-2-indolylmethanols behaved as C4 synthons rather than C3 synthons.

The synthesis of functionalized linear polysiloxanes has garnered considerable attentions due to their broad applicability. While the selective C−H bond functionalization of dimethylsiloxane monomers or polymers offers a promising and versatile approach, it remains a significant synthetic challenge. In this study, we report a mild and efficient iron-catalyzed method for the C−H bond alkylation of both dimethylsiloxane monomers and polysiloxane using polar alkenes as coupling partners. This protocol exhibits broad substrate scope, tolerating a wide range of siloxane/silane substrates and polar alkenes. A variety of functional groups, including amide, ester, ketone, and nitrile, can be readily introduced into the siloxane framework. Functionalized polysiloxanes are accessible either through direct C−H bond functionalization or via copolymerization using the modified monomers. Notably, nitrile-functionalized polysiloxanes display significant photoluminescence properties, offering new opportunities for expanding the application scope of polysiloxane materials. Based on experimental studies, a plausible catalytic mechanism is also proposed.

The first iron-catalyzed asymmetric hydrosilylation of α-substituted vinylsilanes is reported. This reaction proceeds with high regio- and enantioselectivity, providing an efficient access to enantioenriched chiral vicinal bis(silane)s bearing derivatizable Si–H bonds. Importantly, the localized steric bulky effect in the new designed ligand significantly enhances both yield and enantioselectivity. Furthermore, gram-scale synthesis could be performed smoothly. The derivatizations of the resulting chiral vicinal bis(silane)s are also demonstrated, furnishing high-value cyclosiloxane and siloxane.

Electrochemical rearrangement reactions represent one of the most versatile types of organic chemical transformations, which afford efficient strategies for the rapid construction of complex molecular skeletons. However, known achievements in electrochemical rearrangement of alkene compounds are mainly focused on the migration of radical species. Thus, the development of new electrochemical rearrangement modes, in particular, remote migration rearrangement, is in high demand but still remains a great challenge. Herein, we report a novel electrochemical rearrangement reaction of acryl imides in the presence of nBu₄NI and water, which proceeds via nucleophilic substitutions leading to skeletal editing and affording α,β-dihydroxyl amides with up to 76% yield. Control experiments suggest that this reaction proceeds through oxidation of iodide anion, iodination of alkenyl bond, coupling with water, substitution to form epoxide, substitution ring-opening, and intramolecular substitution to afford the desired dihydroxyl amides. This work represents a new electrochemical rearrangement mode and provides a new and efficient strategy for the synthesis of α,β-dihydroxyl amide derivatives.

Solid-state structures and aromaticity of open-shell cycloparaphenylene (CPP) dications remain elusive. This work reports the first isolation of open-shell cycloparaphenylene dications [9]CPP^2•2+ and [11]CPP^2•2+ through weakly coordinating anion-stabilized oxidation. X-ray crystallography confirms radially oriented π-delocalization, while EPR/SQUID analyses reveal antiferromagnetic coupling in open-shell singlet ground states with significant diradical character. Bidirectional aromaticity modulation emerges upon oxidation: diminished local benzene character versus enhanced global in-plane aromaticity, with macrocycle size governing diradical stability (ΔE_OS-T, –3.11, –1.30, –0.99 kcal·mol^–1 for [9]CPP^2•2+, [10]CPP^2•2+ and [11]CPP^2•2+, respectively). Remarkably, size expansion preserves local aromaticity while reducing macrocyclic aromaticity, demonstrating electronic control over geometric constraints. These 3D spin-delocalized systems bridge Hückel aromaticity with curved π-topology, offering design principles for carbon nanotube-inspired organic spintronics and molecular multielectron storage architectures.

Whether the fluorine atom (F) can engage in a halogen bond (XB) has remained a subject of ongoing debate. The discovery of N-fluoropyridinium triflate as a unique "F-cation organocatalyst" for aziridine synthesis has generally been considered the first instance of F-halogen bonding catalysis. Nevertheless, the mechanistic details of this reaction have remained elusive, and compelling evidence supporting the F-halogen bond catalysis has been lacking. In this study, we present an in-depth computational investigation of the mechanism of this reaction to gain insights into the intriguing role of the F-cation organocatalyst. Our results, however, are inconsistent with the previous prevalent F-halogen bonding catalysis mechanism but instead, bring to light a new fluorine cation transfer mechanism. This novel mechanism is supported by control experiments and can explain the observed cis-trans selectivity.

Silylation of C–H bond has been established to be an important strategy toward construction of complex organosilicons. Still, the state-of-the-art is mostly limited to intramolecular reactions or limited to employment of thiophenes or reactive arene reagents. Herein, rhodium-catalyzed intermolecular C–H silylation of indoles has been realized using silacyclobutanes as a silylating reagent, affording a variety of C2-silylated indoles. This chelation-assisted C–H silylation system proceeds well with a broad substrate scope with 100% atom-economy.

The noncovalent interaction-assisted transition metal catalysis has attracted intense interest, and emerged as a powerful tool to develop new privileged ligands. Herein, we developed a library of novel mantis-shaped bifunctional chiral monodentate-type phosphine ligands having octahydroindole-imidazolone skeleton as the key stereodirecting monochiral arm and the tertiary amine group as an H-bond acceptor, namely OPI-Phos ligands, which were prepared from the optically pure easily accessible octahydroindole-amides in one step. These ligands are characteristic of easy synthesis, rigid backbone, high tunability and air stability. They were proven to be a class of efficient chiral ligands for Pd-catalyzed asymmetric allylic substitution reactions of rac-allyl acetates with O and C-nucleophiles, achieving high reactivity and enantioselectivity. Single crystal structure of OPI-Phos ligand/palladium complexes revealed a possible monodentate manner-type reaction mechanism.

We herein describe an enantio- and diastereoselective rhodium(I)-catalyzed defluorinative arylation of pentafluoroethyl alkenes with arylboronic acids. A new class of previously inaccessible functionalized fluoroalkenes featuring a sp²-carbon connected to F and CF₃ can be synthesized. Using both 1,1- and 1,2-disubstituted alkene substrates, tetra- and trisubstituted fluoroalkene products are obtained in excellent Z/E selectivities with well-defined alkene geometry. These fluoroalkenes are potential synthons for accessing chiral compounds containing a stereogenic centre with F and CF₃ group.

Construction of biologically interesting tryptanthrin-derived N,O-ketals was enabled via Cu(II)-catalyzed enantioselective addition of alcohols and tert-butyl hydroperoxide to tryptanthrin-derived N-Boc ketimines. Stereoselective activation of the electrophiles was possible using structurally confined chiral catalysts although such electrophiles suffered from the drawbacks such as low reactivity or steric hindrance around the reaction center. The protocol tolerated variations in both the tryptanthrin part and the alcohol scopes, and the products could be obtained with up to 99% ee and in up to 99% yield. Gram-scale reaction was possible, and functional group transformations could also be realized. X-ray diffraction experiments confirmed the configuration of tryptanthrin-derived N-Boc ketimine as well as the absolute configuration of the product.

LiCoO₂ (LCO) is a widely used cathode material for lithium-ion batteries due to its high specific capacity and good rate capability. However, its practical application at high voltages (≥4.6 V) is severely limited by several critical issues, resulting in poor cycle stability and capacity fading. To address these challenges, LCO with LaF₃ & LaOF nanophases modification was synthesized via a solid-state method, based on a synergetic strategy applying LaF₃ fast-ion-conducting coating to improve the interfacial ionic transport meanwhile constructing corrosion-resistant LaOF to suppress degradation. Through the electrochemical performance tests at high voltages (≥4.65 V), the optimal LCO-0.2LaF possesses superb high-voltage electrochemical performance: the initial capacity equals 193.0 mA·h·g^–1 with the retention of 91.1% after 100 cycles (1 C, 3.0–4.65 V); even at 1 C (3.0–4.70 V) the initial capacity is 207.7 mA·h·g^–1 and the retention is 76.6% after 100 cycles. Structural characterizations, including in-situ XRD, SEM, HRTEM, and XPS, etc., reveal that the synergetic modification of LaF₃ and LaOF nanophases can effectively suppress O^2– peroxidation, Co dissolution and the drastic contraction and expansion of the lattice, thereby inhibiting the irreversible H3 → H1-3 → O1 phase transition above 4.65 V.

Porous organic polymers (POPs) have shown great potential as organic cathode materials (OCMs) for advanced lithium-ion batteries (LIBs). However, OCMs still face challenges such as insufficient output voltages. In this work, we report the design and synthesis of two dihydrophenazine-based POPs (denoted as TPBPA-DHP and PPT-DHP) with multiple p-type redox-active sites. When employed as OCMs for LIBs, both TPBPA-DHP and PPT-DHP cathodes exhibit high voltage platform characteristics, achieving ultrahigh output voltages of 3.59 and 3.61 V, respectively, along with remarkable energy densities of 536.8 and 502.1 Wh·kg^–1. Benefiting from their highly crosslinked structures and robust skeletons, both POP cathodes exhibit long cycle stability, retaining 72.7% and 70.8% of their capacities after 1000 cycles at 0.5 A·g^–1. Ex situ FT-IR spectra and EPR measurements were conducted to elucidate the redox mechanism involving anion interactions with p-type redox-active centers. Moreover, the PPT-DHP//graphite full cell delivers a high average discharge capacity of 129.2 mAh·g^–1 at 0.1 A·g^–1, retaining 76.9% of its initial capacity after 1000 cycles at 0.5 A·g^–1. This study provides valuable insights into the molecular design and synthesis of p-type POPs for the next generation high-voltage LIBs.

Eneyne is one of the most prevalent building blocks in synthetic chemistry. Alkenyl C−H alkynylation affords an efficient synthesis of eneynes, however, the direct use of styrenes as the synthon has remained much unexplored so far. We present the first α-/β-C−H alkynylation of E- and Z aryl alkenes as well as α-substituted aryl alkenes, producing complex eneynes with excellent regio- and E/Z ratio selectivity, assisted by N,N-bidentate directing group under palladium catalysis. Notably, disubstituted E-aryl alkenes underwent α-C−H alkynylation and then β-C−H alkenylation to produce conjugated dieneynes. The robustness of the protocol was further demonstrated by the successful C−H conversion of substrates including 2-alkenyl benzyl amides and anilides, proceeding by five- to seven-membered endo-/exo-palladacycles.

Alkylamines play an important role in medicinal chemistry, while carboxylic acids are commonly found in many natural products and pharmaceuticals. In this study, we developed a direct photoredox-catalyzed decarboxylative amination of alkyl carboxylic acids using a novel N-centered radical scavenger. This method avoids pre-activation and transition-metal catalysts, allowing a diverse range of readily available carboxylic acids to be efficiently converted into medicinally valuable amines. Further mechanistic studies and DFT calculations were conducted to provide evidence for the proposed photoredox-catalyzed pathway. This protocol is operationally simple and has excellent functional group compatibility, which is likely to be of great use in synthetic chemistry

A bis-carbene iridium catalyst with a unique structure, featuring a straightforward synthetic route and low-cost ligands was developed. This catalyst exhibits high catalytic activity in the Julia-type olefination reactions between sulfone compounds and benzyl alcohol derivatives, with catalyst loading reduced to as low as 0.5 mol%. Furthermore, by adjusting the reaction conditions, the resultant olefinic products can be further reduced in a single step to afford the corresponding alkane compounds. This study also explores the reaction mechanism, proposing a plausible catalytic cycle based on a series of control experiments.

RNA modifications have revealed essential regulatory roles in messenger RNA (mRNA) metabolism to affect cellular gene regulation, and have also received widespread applications in RNA therapeutics such as mRNA vaccine and protein replacement. Most efforts focus on mRNA internal base and ribose modifications, however, chemical modification within mRNA poly(A) tail remains unexplored. In this work, we synthesized luciferase and GFP (Green Fluorescent Protein) mRNAs with a fully chemically modified poly(A) tail, in which adenosine is replaced by either base-modified N⁶-methyladenosine (m⁶A)/N⁶-ethyladenosine (Et⁶A) or ribose-modified 2’-O-methyladenosine (Am), and investigated the effect of these tail modifications on mRNA stability and translation efficiency upon transfection into cells using fluorescent and chemiluminescent reporter assays. The results showed that all these modifications impaired translation without affecting mRNA stability. Further study demonstrated that modified poly(A) tail weakens its binding to PABPC1 (Polyadenylate-Binding Protein 1), which reduces the formation of mRNA head-to-tail loop and thus decreases the translation efficiency. Our finding reveals the translation-regulatory role of the adenosine modifications within poly(A) tail, offering a new way for manipulating mRNA translation inside cells.

Given the ubiquity of amines in natural products, pharmaceuticals, and functional materials, the development of facile deamination methods offers a promising strategy to increase the diversity of chemicals in drug discovery. In this study, we design and synthesize a novel deamination reagent, N-(benzyloxy)-N-(isobutyryloxy)-4-nitrobenzamide, leveraging its unique properties to efficiently convert readily available primary amines into diverse aromatic and heteroaromatic compounds, aliphatic hydrocarbons, and alkyl esters. This method exhibits broad functional group tolerance, including carbonyl, alkynyl, and amino groups, and has been successfully applied to amino acids, peptides and marketed drugs. Furthermore, the scalability of the reaction, as well as its utility in the sequential functionalization/deamination modification and deutero-deamination of various primary amines, highlights the practical potential of this approach.

We report a transition-metal-free and bis(pinacolato)diborane (B₂Pin₂)-promoted transfer hydrogenation of various alkynes to alkanes in high yields with methanol as hydrogen source under mild reaction conditions. Control experimental results revealed that bis(pinacolato)diborane and methanol played important roles for the transfer hydrogenation of alkynes to alkanes. It is shown that in situ generated borane was the key reductant for the activated alkynes whereas bis(pinacolato)diborane served as strong Lewis acid reagents for diarylacetylenes. More importantly, these transfer hydrogenations could be applied into modifying natural products and a CF₃-substituted alkyl group could be easily introduced into complex molecules. The present method highlights mild reaction conditions, broad substrate scope of alkynes, transition-metal free transfer hydrogenation, and gram scalable preparations without column chromatography.

The stereoselective reduction of strained molecules and subsequent synthetic transformations provide an efficient strategy to access multi-substituted carbocycles. These carbocycles are important structural skeletons in natural products and bioactive molecules. We report here a Luche-type enantioselective reduction of cyclobutenones and strained-ring fused cyclic imides. This process utilizes the catalysis of Sc–N,N’-dioxide ligand complex and NaBH₄ as reductant. Moreover, the developed methodology is applicable to the strained olefins, which are not tolerated under metal hydride conditions.

As the aza-isosteres of sulfonyl fluorides, sulfonimidoyl- and sulfondiimidoyl fluorides are versatile and robust SuFEx linkage agents, yet with limited synthetic accessibility. Herein, we report the straightforward, divergent synthesis of sulfonimidoyl- and sulfondiimidoyl fluorides from bench-stable, readily available sulfenamides and Selectfluor. The obtained sulfonyldiiminyl fluorides readily underwent versatile SuFEx reactions with various nucleophiles to afford various biologically interesting sulfondiimidoyl derivatives.

Structurally-modified acenes with a linear fusion of π-extended systems have shown highly attractive properties and promising applications in semiconductor materials, optoelectronic materials and others due to their unique electronic structures. We have accessed a series of anthra/tetra/pentaquinodimethane-supported organoboranes, Mes*B-A, Mes*B-T and Mes*B-P, with highly tunable emissions from blue to red (~680 nm) by controlling the number of fused benzene rings of the [n]acene core (n = 3–5). Interestingly, these redox-switchable quinoid systems have chemically and electrochemically enabled two-electron oxidations, leading to dicationic anthracene, tetracene and pentacene segments (Mes*B-A²⁺, Mes*B-T²⁺ and Mes*B-P²⁺) as evidenced by new absorption bands in the UV−vis−NIR spectra and spectroelectrochemical studies. Meanwhile, all the molecules feature a π-conjugated, overcrowded ethylene structure that allows for a spin-state transition from closed-shell to the open-shell diradicals (Mes*B-A^2•, Mes*B-T^2• and Mes*B-P^2•) under thermal conditions. This can further be confirmed by the variable-temperature (VT) ¹H NMR and electron spin resonance (ESR) spectroscopy. These organoboranes also experienced an emission change in response to fluoride binding with electron-deficient boron centers. Our current work demonstrates not only the synthetic contribution to [n]acene-based luminescent materials, but also showcases multistate transformations for potential applications depending on well-tuned electronic, magnetic, electron transfer and charge transport mechanisms.

Fluoroalkoxylated heterocycles, such as indoles, holds significant importance in pharmaceuticals and biology. Herein, we report a copper-mediated C4–H fluoroalkoxylation reaction of indoles via a transient directing group (TDG) strategy. This reaction exhibits excellent regioselectivity and broad functional group compatibility, offering a new approach for the synthesis of fluoroalkoxylated indoles. The reaction also represents an unprecedented example of 3d-transition metal-catalyzed C─H fluoroalkoxylation via a TDG strategy.

As readily available and abundant industrial feedstocks, alkenes have emerged as versatile platform for constructing value-added targets. Transition metal-catalyzed dicarbofunctionalizations reactions forge two carbon-carbon bonds in one step with construction of two vicinal saturated carbon centers, providing profound synthetic potential in organic synthesis and pharmaceutical chemistry. In particular, nickel-catalyzed reductive dicarbofunctionalization of alkenes has witnessed remarkable progress in recent years. Compared to conventional redox-neutral dicarbofunctionalization strategy, reductive variant offers significant advantages, such as no use of pre-formed organometallic reagents, operational simplicity and mild reaction conditions. This review summarizes developments of nickel-catalyzed reductive dicarbofunctionalization of alkenes to forge diverse carbon-carbon bonds in the absence of stoichiometric carbon nucleophiles. The mechanistic considerations are comprehensively discussed, including two-electron migratory insertion and the single-electron radical addition pathways. Furthermore, we provide critical insights into future directions and potential challenges in this area, highlighting opportunities for further methodology development and applications for nickel-catalyzed reductive dicarbofunctionalization of alkenes.

Three-dimensional (3D) molecular nanocarbons have garnered significant attention due to their unique properties, including chirality, aromaticity, and photovoltaic behavior, which arise from their complex 3D structures. These characteristics make them promising candidates for a wide range of applications. This review provides an overview of recent developments in the synthesis, structural features, and functional applications of these materials, highlighting their potential in various fields of chemistry and materials science.

The catalytic difunctionalization of alkenes offers an efficient and straightforward approach to incorporating two functional groups across a double bond for increasing molecular complexity and has found widespread application in organic synthesis. Among them, photo-/electrocatalytic difunctionalization of alkenes based on the radical-polar crossover strategy has gained increasing attention. This approach not only aligns with the principles of green and sustainable chemistry but also uniquely merges both radical and ionic modes of reactivity, overcoming the inherent limitations of conventional methodologies. This review summarizes the innovative progress in photo-/electrocatalytic difunctionalization of alkenes over the last decade, which is focused on the transformations via oxidative radical-polar crossover (ORPC) or reductive radical-polar crossover (RRPC) as the key step and particular emphasizes on the selection of functionalized polar adducts.

Hydride superconductors are promising candidates for high-temperature superconductivity across a wide pressure range. This review presents a comprehensive review of their structural, electronic, and superconducting properties, with a focus on how pressure influences phase stability and enhances critical temperature (T_c). We categorize hydrides into three pressure regimes: ambient pressure, low pressure (<100 GPa), and high pressure (>100 GPa). Ambient pressure compounds, such as perovskite-like hydrides and SM₂TMH₆ structures, exhibit moderate T_c values. Low-pressure hydrides benefit from unique strategies like molecular doping and electron precompression to improve their T_c. The high-pressure hydrides exhibit higher T_c values, including room-temperature superconductivity, but require extreme conditions for synthesis and characterization. We also highlight recent theoretical and experimental advances, outlining current challenges and prospects. This review not only highlights the potential of hydride superconductors but also provides a roadmap for future research in this exciting and rapidly developing field.

Proteins are widely used in hydrogel materials due to their excellent biocompatibility, precisely controllable sequence structures, and diverse biochemical and mechanical properties. In recent years, numerous protein hydrogels with tailored mechanical performance have been developed to mimic the mechanical properties of biological tissues such as muscles and cartilages. However, systematic guidelines for the rational design of mechanical properties in protein hydrogels remain scarce. In this review, we comprehensively summarize recent advances in protein hydrogels and explore design strategies for various mechanical properties such as stiff, tough, and fast-recovery protein hydrogels by focusing on crosslinking and hydrogel networks. Subsequently, we briefly summarize the biomedical applications of protein hydrogels. Notably, we discuss the relationship between protein mechanics at the molecular level and bulk hydrogel properties, and highlight the potential of artificial intelligence in guiding protein building block construction and hydrogel design.

In 1998, Tirrell et al. first utilized recombinant proteins in hydrogel preparation by synthesizing reversible protein hydrogels through the physical interactions of leucine zipper domains. This was followed in 1999 by Jindřich Kopeček's development of hybrid hydrogels assembled from synthetic polymers and coiled-coil protein domains, jointly marking the inception of research into recombinant protein-engineered hydrogels. In 2002, David J. Mooney and colleagues covalently conjugated RGD peptide sequences to alginate, a polysaccharide hydrogel matrix, resulting in protein–polysaccharide hydrogels that significantly enhanced chondrocyte and osteoblast adhesion and proliferation, thereby promoting bone tissue regeneration and establishing a benchmark in tissue engineering. In the same year, Timothy J. Deming et al. synthesized diblock copolypeptide amphiphiles comprising charged and hydrophobic segments; the resulting hydrogels exhibited robust mechanical integrity at temperatures up to 90 °C and rapid recovery following stress relaxation. In 2003, David Baker and his team pioneered the field of de novo protein design by creating the protein Top7, later developing numerous de novo proteins for hydrogel fabrication that overcame the limited functionality of natural proteins and enabled precise control from molecular structure to macroscopic mechanics. In 2005, Dixon and Elvin prepared highly elastic hydrogels via photochemical crosslinking of recombinant resilin, catalyzing widespread interest in elastic protein-based materials. In 2006, Hubbell and colleagues incorporated cell-adhesive motifs and protease-sensitive sequences into recombinant protein backbones, which were chemically crosslinked with polyethylene glycol (PEG) to form hydrogels with enhanced biological activity and degradability—representing the first successful integration of functional recombinant protein domains with synthetic polymers. In 2008, Chilkoti et al. designed the first elastin-like polypeptides (ELPs)-based hydrogels by reacting ELPs with β-[tris(hydroxymethyl)phosphino] propionic acid, which were later developed into thermoresponsive, injectable protein hydrogels. In 2009, Heilshorn et al. introduced protein–protein interactions into hydrogel design, creating a mixing-induced two-component hydrogel (MITCH) based on WW domain and proline-rich motif interactions, enabling applications in neural stem cell culture. In 2010, Li et al. linked GB1 domains with resilin to mimic titin, yielding hydrogels with high toughness and fast recovery that reproduced the mechanical behavior of muscle; in 2023, they further advanced this platform to generate protein hydrogels with dense chain entanglement capable of simulating cartilage mechanics. Also in 2010, Khademhosseini demonstrated the strong potential of gelatin methacrylate (GelMA) as a micropatterned cell culture substrate that supported rapid adhesion, proliferation, and migration. In 2011, Kiick et al. developed modular recombinant resilin-like polypeptides (RLPs) and crosslinked them with β-[tris(hydroxymethyl)phosphino] propionic acid to produce hydrogels with excellent and tunable mechanical properties, establishing RLPs as promising bioactive materials. In 2012, Yang et al. engineered a tetrameric protein crosslinker with high affinity for peptide nanofiber termini, significantly enhancing the stiffness of supramolecular hydrogels. In 2015, DeForest et al. employed two orthogonal photochemical bio-click reactions to dynamically pattern proteins within three-dimensional hydrogels, enabling precise spatiotemporal control of stem cell differentiation. In 2017, Stevens et al. developed a β-sheet peptide–poly(γ-glutamic acid) hybrid hydrogel with tunable mechanics and self-healing properties through physical crosslinking by grafted β-sheet peptides; in the same year, Sun et al. reported a B12-dependent photoresponsive protein hydrogel designed for controlled release of stem cells and proteins, where polymeric CarHC proteins self-assembled into elastic hydrogels in the dark and disassembled upon light exposure—offering a general strategy for dynamically tunable protein materials. In 2018, Cao and his team established a framework for rational design and prediction of hydrogel mechanics by tuning the molecular stability of crosslinkers and load-bearing modules, leading to the creation of strong, tough, fast-recovering, and fatigue-resistant hydrogels via mechanisms including metal coordination, tandem crosslinkers, and force-triggered hidden length release; concurrently, Zhang et al. used split intein-mediated protein assembly to biosynthesize high molecular weight proteins like spider silk and mussel foot proteins, yielding materials with greatly enhanced mechanical properties. In 2020, Zhang et al. pioneered slide-ring protein hydrogels using artificially designed lasso proteins, demonstrating the utility of topological protein engineering for hydrogel design. From 2020 to 2024, Liu et al. developed a series of strong and tough protein-based materials, including fibers and bioadhesives, providing multiple strategies for high-performance protein material design. In 2021, Holten-Andersen et al. introduced an in situ mineralization strategy at metal coordination crosslinking sites—such as Ni²⁺/Cu²⁺–histidine and Fe³⁺–catechol—to enhance hydrogel stiffness and durability via nanoparticle nucleation. Most recently, in 2023–2024, He and colleagues strengthened gelatin hydrogels through cyclic mechanical training, creating anisotropic, hierarchical structures with high tensile strength, thus expanding the mechanical versatility of protein hydrogels.