The preparation of polyethylene with well-defined microstructures and precise molecular weights has been a long-standing challenge in olefin polymerization. Despite the complexity of this task, the rational modification of transition metal catalysts continues to be the primary strategy for addressing these limitations. Here, we reported the synthesis of a series of multifunctional amine-imine nickel(II) complexes bearing ortho-substituents (X = –SO₂Ph, –COOMe, –POMe₂) on the ligand framework and systematically investigated the influence of adjacent functionalities on ethylene (co)polymerization performance. In ethylene polymerization, these nickel(II) complexes demonstrated high activities (up to 7.00 × 10⁵ g_PE·mol_Ni^–1·h^–1), affording polyethylene with high molecular weights (M_n up to 4.75 × 10⁵ g·mol^–1) and tunable branched microstructures (70–108/1000C). The resulting polymers displayed excellent elastomeric properties with a high tensile stress-at-break of 34.0 MPa and strain-at-break of 1032%. Notably, the complex containing POMe₂ achieved controlled living polymerization of ethylene, exhibiting precise molecular weight control and narrow dispersity (Đ ≤ 1.10). In addition, these nickel(II) complexes successfully mediated the copolymerization of ethylene with 10-undecenoate and 10-undecenoic acid to prepare the functionalized polyolefins. These results suggest that the incorporation of ortho-coordinating groups may hinder the toxicity of polar functional groups to the metal center, thereby enhancing the catalyst's tolerance to polar substrates.

The relentless drive toward miniaturization in the semiconductor industry demands photoresists capable of patterning sub-20 nm features for next-generation extreme ultraviolet (EUV) lithography. Metal-oxo clusters, with sub-5 nm molecular dimensions, structural tunability, and high EUV absorption via metal centers, have emerged as promising EUV photoresist candidates. Advancing next-generation photoresist materials necessitates resolving the inherent trade-offs between sensitivity, resolution, and line-edge roughness. In this work, we report a series of halogenated metal-organic clusters based EUVL photoresists, aiming to modulate the sensitivity, resolution, and line-edge roughness. Here, we report the synthesis of halogenated metal-organic clusters as EUVL photoresists, designed to modulate the resolution-line edge roughness-sensitivity trade-off. Sub-20 nm critical dimensions and line edge roughness below 2 nm were achieved with the clusters by EUVL. The results demonstrated that halogen elements influenced the sensitivity of the clusters. To unravel the EUV-driven reaction pathways, we analyzed the chemical transformations in these clusters after exposure using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy. These findings pave the way for the rational design of high-performance EUV photoresists.

Despite significant progress in catalytic asymmetric synthesis of chiral allenes via homogeneous or heterogeneous metal-catalyzed, photoexcited metal-catalyzed as well as certain exquisite organocatalytic asymmetric methods, the asymmetric syntheses of chiral allenes via organo-phosphines catalysis are rare. In this paper, a catalytic asymmetric conjugate addition of malonic esters to yne-enones was successfully achieved via coperative catalysis of chiral biamide-phosphine and methyl acrylate, which afforded the corresponding chiral trisubstituted 1,2-allenyl ketones containing contigous axial and carbon center chirality with excellent enantioselectivity (up to 99% ee) and good diastereoselectivity (up to 93 : 7 dr). It is meaningful to note that the addition of an inorganic base (K₂CO₃) did not cause the background racemic reaction but could enhance the reactivity as a co-catalyst. The developed protocol demonstrates a wide range of substrates, high tolerance to various functional groups, versatile product functionalization and ease of operation as well as mild reaction conditions. Additionally, this coperative catalytic mode will not only promote the design of novel chiral phosphine catalysts, but also shine some light on expanding the reaction scope of asymmetric phosphine catalysis.

Radical-mediated difunctionalization of alkenes has attracted intensive attention from the synthetic community in recent years. Carbon radicals play a pivotal role as reactive intermediates in alkene difunctionalization reactions, showcasing remarkable potential in forging both carbon-carbon and carbon-heteroatom bonds. Traditionally, these transformations proceed through the merger of the classical transition metal catalysis, employing metals such as Ag, Ni, Fe, Cu, and among others. Recently, photoredox catalysis has emerged as a powerful tool for enabling challenging molecular transformations and accessing previously inaccessible chemical space in an environmentally benign and mild manner. In the present work, a novel visible-light-induced copper/photoredox dual catalysis for intermolecular multicomponent difunctionalization of alkenes with aqueous sulfoxonium ylides and versatile functional groups has been developed. This reaction system utilizes alkenes and sulfoxonium ylides as easily prepared starting materials, operates under facile and sustainable conditions, and does not require the addition of acids or bases. Furthermore, the scalable protocol allows for the incorporation of a wide array of alkenes, sulfoxonium ylides, and external protic nucleophiles, including water, chloride, bromide, azide, and thiol. The general system provides a viable access to structurally C(sp³)-rich γ-hydroxylketones, organic halides, organic sulfides, and azide compounds with excellent chemo- and regioselectivity. Mechanistic investigations imply that two distinct reaction pathways are involved in the generation of carbon radicals from sulfoxonium ylides through a mild visible-light-driven proton-coupled electron transfer (PCET) strategy in the absence or presence of copper salts. This dual catalytic system will establish a novel paradigm, thereby expanding the scope of carbon radical-mediated transformations of olefins.

A bifunctional squaramide-catalyzed asymmetric synthesis of chiral tricyclic chromans featuring three contiguous stereocenters has been successfully developed. This innovative strategy relies on the synergistic activation of 3-aminophenol derivatives and 4-benzylidenepyrrolidine-2,3-diones by the chiral catalyst, enabling an efficient asymmetric oxa-[3+3]-annulation reaction. The protocol exhibits a broad substrate scope with 34 diverse examples, delivering moderate-to-good yields ranging from 64% to 81%, excellent enantioselectivity (up to 99% ee), and tunable diastereoselectivity (dr up to 15 : 1). Notably, halogen substitution plays a pivotal role in dramatically enhancing stereocontrol, further optimizing the diastereoselectivity of the target products. To validate its practical utility, gram-scale synthesis was successfully conducted without compromising yield or stereoselectivity, and subsequent derivatization reactions confirmed the versatility of the obtained chiral tricyclic chromans. This metal-free, mild reaction system not only enriches the synthetic toolbox for constructing complex chroman architectures, but also provides a versatile platform for the asymmetric synthesis of bioactive molecules containing the chiral tricyclic chroman skeleton, highlighting the significance of enantioselectivity and diastereoselectivity in accessing functionalized heterocyclic compounds.

Herein, a pair of hydrazone-linked covalent organic frameworks (COFs) were constructed with identical main-chain backbone and distinctive side chains (denoted as BTB-COF and BTD-COF), respectively. With H₂PtCl₆ as the co-catalyst precursor, BTD-COF with ethoxy side chains demonstrated superior photocatalytic H₂ production performance yielding 3708 μmol·g⁻¹·h⁻¹ under visible light irradiation, which was 3.0 times higher than that of its analogue BTB-COF with thioether side chains (1236 μmol·g⁻¹·h⁻¹). Comprehensive studies on the composites of platinum nanoparticles (Pt NPs) with COFs after photocatalytic H₂ generation had revealed the impacts of side chains on the photocatalytic process and the anchoring of Pt NPs within COFs. By contrast with the divalent oxidized-state of Pt on BTB-COF, Pt NPs anchored on BTD-COF existed as metallic Pt⁰ with an uniform size of 2.7 nm, agreeing well with the diameter of pore channels. The nature of metallic Pt⁰ NP was greatly beneficial for the surface charge transfer process and had consequently enhanced the photogenerated carrier separation efficiency, which was supported by the density functional theory calculations. This work elucidates the impacts of side chains on the H₂ generation performance of COFs under visible light, which will further spur the structural evolution of functional COFs materials.

Chiral metal-organic clusters (cMOCs) are characterized by diverse chiral origins, tunable luminescence, and multifunctionality. Among them, chiral aluminum oxo clusters (AlOCs) exhibit unique advantages in terms of resource sustainability and environmental friendliness compared to other cluster materials. Nevertheless, the simultaneous achievement of precise enantiomeric control and optical response within AlOCs remains a critical challenge to be addressed in the field. Herein, we achieve precise control over the transition from chirality to circularly polarized luminescence properties in AlOCs by leveraging their highly flexible and modifiable coordination surfaces through a stepwise ligand functionalization strategy. We employed the Al₂ cluster as a platform with programmable surface coordination sites and introduced classical chiral L/D-valine molecules. We successfully constructed four pairs of alcohol-coordinated pure chiral enantiomers (AlOC-189-L/D-MeOH, EtOH, PrOH, and PDO). Absolute helical structures can be identified in the supramolecular architectures of clusters, achieving unambiguous chirality transfer from chiral ligands to chiral clusters and further to absolute helical superstructures. Hierarchical ligand modification, endowed with a top-down design paradigm, offers a rational and feasible route to cluster functionalization. Based on the excellent replaceability of the Al₂ cluster's surface coordination sites, we achieved chiral-luminescent bifunctional coupling by partially substituting the chiral ligands with π-conjugated naphthyl-based luminophores (HNA/HNN), yielding two new classes of enantiomers (AlOC-190-L/D-HNA and AlOC-190-L/D-HNN) exhibiting bright yellow-green photoluminescence (PL). DFT calculations reveal that this is attributed to a ligand-to-ligand charge transfer (LLCT) luminescence mechanism. Notably, AlOC-190-L/D-HNN exhibited promising circularly polarized luminescence (CPL) activity via the synergy between chiral induction from L/D-valine ligands and intermolecular charge transfer of the HNN ligands. This work not only highlights the highly designable coordination chemistry of AlOC—enabling on-demand integration of specific functionalities through modular ligand substitution—but also establishes a novel "ligand editing" paradigm for developing multifunctional chiral optical materials.

The scarcity of critical raw materials in lithium-ion batteries has driven increasing interest in alternative chemistries, such as sodium- based all-solid-state batteries. Among various solid electrolytes, sulfide-based Na₃PS₄ stands out for its high ionic conductivity and excellent formability. However, its poor interfacial compatibility with conventional high-voltage oxide cathodes remains a major limitation. In this study, we report the successful integration of amorphous Na₂MoS₄—a high-capacity, sulfide-compatible cathode—into Na₃PS₄-based all-solid-state sodium batteries. Benefiting from a moderate redox potential window (1.1–2.7 V vs. Na⁺/Na), Na₂MoS₄ exhibits excellent chemical and electrochemical compatibility with Na₃PS₄, as confirmed by structural and spectroscopic analyses. Further investigation reveals that intimate interfacial contact between both electrodes and the solid-state electrolyte is critical for achieving long-term cycling stability. Based on these insights, the optimized Na₁₅Sn₄ | Na₃PS₄ | Na₂MoS₄-Na₃PS₄-carbon nanofiber cell delivers a reversible capacity of ~372 mAh·g^–1 at 0.1 C and retains nearly 100% capacity over 450 cycles at 0.3 C. In situ impedance spectroscopy further confirms the stability of interfacial resistance throughout cycling. This work identifies Na₂MoS₄ as a highly promising sulfide cathode for high-energy, long-life sodium solid-state batteries and provides valuable design principles for future development of sulfide-based electrode-electrolyte interfaces in next-generation energy storage systems.

Developing high-performance, durable, and cost-effective oxygen reduction reaction (ORR) catalysts is essential for advancing next-generation energy devices like zinc-air batteries (ZABs). Herein, we engineer a hybrid Fe-N-C catalyst (FeSA-Fe_NP/CeO₂@NC) integrating atomically dispersed Fe-N_x sites, Fe nanoparticles, and oxygen vacancy-rich CeO₂ nanoparticles within a nitrogen-doped carbon matrix. Interfacial charge transfer and oxygen vacancy-mediated electron redistribution, synergistically enhanced by strong metal-support interactions (SMSI), optimize the electronic configuration of Fe-N_x sites and reduce their electron density. The resulting catalyst exhibits exceptional ORR activity and stability, featuring a half-wave potential of 0.925 V (vs. RHE) in alkaline media and minimal degradation (1% and 2.8% negative shifts after 10,000/20,000 cycles). In ZABs, it achieves a peak power density of 310.29 mW·cm^–2 while sustaining stable operation for over 600 h. This work demonstrates dual role of CeO₂ in enhancing activity and stability, establishing a design principle for high-performance electrocatalysts in energy conversion systems.

The homolytic fragment of the adjacent C(sp³)–C(sp²) bonds in unstrained ketones has proven to be a formidable challenge. Traditional methods for C(sp³)–C(sp²) bond activation typically require harsh reaction conditions, transition-metal catalysts, or specifically designed strained substrates, which largely limit their practical application in organic synthesis. In this study, we develop a visible light photoinduced deacylative C−C and C−S couplings of ketones under mild conditions. This approach leverages the unique reactivity of dihydroquinazolinones, which are easily accessible from commercially available ketones. Upon visible light irradiation, these precursor compounds undergo controlled homolysis to generate open-shell radical species, thereby circumventing the high bond dissociation energy that typically hinders the cleavage of C(sp³)–C(sp²) bonds. The resulting carbon-centered radicals then engage in synthetically diverse cascade reactions with various sulfonyl coupling partners, including sulfonyl oximes, heteroaryl sulfones, and sodium arylsulfinates, enabling the efficient construction of C–C and C–S bonds. This strategy features mild reaction conditions, high efficiency, broad substrate scope and readily accessible starting materials. Mechanistic studies reveal that the process follows a non-chain radical mechanism, where dihydroquinazolinones undergo single-electron transfer (SET) with the excited-state photocatalyst, generating reactive alkyl radicals that engage in subsequent reactions. By transforming simple ketones into versatile radical precursors, our method provides a new platform for reaction design and late-stage functionalization, offering chemists a valuable tool for constructing complex molecular architectures from unstrained ketones.

Quantum dots (QDs) have attracted significant attention in devices such as solar cells and photodetectors. Although polymer-based hole transport layers (HTLs) have been employed in QD devices, their mechanical flexibility remains underexplored and insufficient for wearable applications. Here, we present a novel interlayer design for PbS QD solar cells and photodetectors by incorporating a low-cost thermoplastic elastomer, SEBS (styrene-ethylene-butylene-styrene), into the polymer HTL. The addition of 10 wt% SEBS promotes a more ordered molecular packing of PM6. As a result, PbS QD solar cells achieved a power conversion efficiency of 11.43%, while the corresponding photodetectors exhibited a high specific detectivity of 2.12 × 10¹³ Jones—among the highest reported values. Beyond performance improvements, SEBS significantly enhances the mechanical flexibility of the HTLs. This work presents a new and effective strategy for simultaneously optimizing the optoelectronic performance and mechanical robustness of QD-based devices.

The enantioselective construction of bis-heterocyclic frameworks containing pyrroline and indole motifs is achieved through a cooperative palladium-catalyzed tandem process. This methodology efficiently couples oxime esters and 2-alkynylanilines via a sequential Narasaka-Heck cyclization/Cacchi coupling reaction, providing direct access to complex chiral architectures in high yields with excellent enantioselectivity. The protocol demonstrates broad substrate scope and functional group tolerance. A diverse range of oxime esters, bearing both electron-donating and electron-withdrawing groups, as well as heterocyclic and polyarene substituents, undergo the transformation smoothly, delivering the desired products in 80%–96% yields and up to 98% ee. The reaction also accommodates various ortho-alkynylanilines with para-, meta-, and even sterically demanding ortho-substituents, yielding products with high stereocontrol. Preliminary mechanistic investigations reveal that the reaction is facilitated by a single palladium catalyst operating in synergy with two distinct supporting ligands. The system features two concurrent catalytic cycles: a Pd/Sadphos cycle that drives the enantioselective Narasaka-Heck cyclization of the oxime ester to form the pyrroline ring, and a Pd/Xantphos cycle that mediates the anti-aminopalladation (Cacchi reaction) of the 2-alkynylaniline to construct the indole core. A key transmetallation step between the alkyl-Pd(II) and alkenyl-Pd(II) intermediates from the respective cycles enables the coupling, followed by reductive elimination to furnish the final bis-heterocyclic product. The synthetic utility is highlighted by a gram-scale synthesis without erosion of yield or enantioselectivity, and the product could be readily derivatized to other valuable chiral nitrogen-containing scaffolds. This work establishes a streamlined and efficient route to enantioenriched bis-heterocycles, showcasing the power of single-metal, dual-ligand cooperative catalysis in complex molecule synthesis.

Despite the widespread use of allyl bromides in organic synthesis, the asymmetric transformation of allyl bromides has been less developed. To date, the asymmetric transformation of allyl bromides has been limited to single-site functionalization, and the development of dual-site asymmetric functionalization remains unexplored. In this work, the unprecedented asymmetric dual-site functionalization of allyl bromides has been realized through an efficient organocatalytic system, overcoming the persistent limitation of single-site transformations. Employing dinucleophiles including 3-aminobenzofurans, 2-aminoindoles, and cyclohexane-1,3-diones, this methodology affords benzofuro[3,2-b]pyridines and α-carbolines in good yields with excellent stereoselectivity. The transformation proceeds via a chemoselective S_N2′ pathway mediated by a chiral pyrrolidinyl sulfonamide catalyst, which generates ammonium salts in situ to achieve stereocontrol. The protocol was successfully extended to enantioenriched privileged pyran frameworks, and was applied to diverse downstream transformations. Gram-scale synthesis maintained high enantioselectivity, confirming practical utility. This approach effectively addresses key challenges in efficient construction of complex fused-ring heterocycles, substantially expanding the synthetic applications of allyl bromides.

The incorporation of solid additive in photoactive layer as an effective strategy has been successfully employed to optimize the formation of a bi-continuous interpenetrating network morphology in blend bulk heterojunction, which is a critical determinant of photovoltaic performance in organic solar cells (OSCs). However, the influence of additive side-chain length on the morphological evolution remains insufficiently understood. In this work, we propose two novel solid additives, 1,3,5-tribromobenzene (TBB) and 1,3,5-tris(bromomethyl)benzene (TBMB) with different side-chain lengths. Theoretical calculations reveal that TBMB, featuring longer side-chain length, demonstrates stronger non-covalent intermolecular interaction with donors and acceptors compared to TBB, thereby favoring optimized molecular aggregation and crystallization behavior during film formation. As a result, the TBMB-treated device achieves a champion power conversion efficiency (PCE) of 17.92% in PM6:Y6 system, outperforming the TBB-treated counterpart (17.20%). Remarkably, TBMB exhibits universal effectiveness across other systems, achieving an exceptional efficiency of 20.04% in D18:L8-BO-based device. This work provides deep insights into the potential working mechanism of solid additives with precise side-chain length modulation, establishing a valuable additive side-chain effects for future research on morphology regulation in OSCs.

C-Acyl glycosides are versatile building blocks for diverse C-glycosides, including hydrazone, alcohol, CF₂, and alkyl variants. However, the relatively late discovery of these in natural products and their overlooked medicinal value have resulted in significantly underdeveloped synthetic methodologies compared to other C-glycoside subtypes. Previously, the synthesis of C-acyl glycosides primarily depended on metal reagent-based addition-oxidation reactions and palladium-catalyzed cross-coupling reactions. As research advances, transition-metal (TM) catalyzed cross-coupling reactions involving glycosyl radicals have emerged as a powerful tool to access C-glycosides (C-acyl glycosides included) due to their advantages such as mild reaction conditions and controllable stereoselectivity. While recent years have seen a boom of cooperative catalysis of transition metals (particularly Pd) and chiral phosphoric acid (CPA), the analogous cooperative catalysis employing nickel (Ni) and CPA remains underdeveloped. Herein, we report a robust Ni/CPA co-catalyzed protocol for synthesizing diverse C-acyl glycosides under mild conditions. This strategy employs readily available glycosyl bromides and amides, 2-pyridyl esters, or phosphoric anhydrides, demonstrating broad functional group compatibility. A wide range of mono- and disaccharides and functionalized carboxylic acid derivatives were efficiently transformed into the corresponding products with high yields (up to 98%) and excellent stereoselectivity (α : β > 19 : 1). Furthermore, the utility of the methodology was demonstrated through the C-acyl glycosylation of various bioactive molecules and the synthesis of C-acyl disaccharides. Remarkably, the cooperative Ni/CPA catalysis significantly enhanced the yield compared to reactions without CPA. Mechanistic investigations revealed that the reaction proceeds via a nickel-catalyzed sequential addition mechanism, while DFT calculations have furnished theoretical support for the proposed pathway whereby CPA enhances the yield through hydrogen-bonding interactions.

The influence of charges on cell membrane-incorporation behaviors of channel proteins remains incompletely understood due to the structural complexity of these proteins. In this study, the influence was investigated by using asymmetric unimolecular artificial channels as simplified models. The study revealed a profound influence of terminal charge on interaction strength and kinetics. The negatively charged Ch⁻ exhibited significantly stronger interactions with lipid bilayers, demonstrated by an 83% membrane incorporation efficiency, compared to only 16% for the positively charged Ch⁺. Fluorescence correlation spectroscopy (FCS) and confocal microscopy confirmed that Ch⁻ rapidly inserts and redistributes within the membrane, while Ch⁺ shows slow, sporadic incorporation, attributed to electrostatic repulsion from positively charged lipid headgroups. Furthermore, the terminal charge critically dictated the channel's orientation within the bilayer. Using a fluorescence quenching assay, it was revealed that Ch⁻ predominantly adopts an outward-facing configuration (83%). In contrast, Ch⁺ favors an inward-facing orientation (only 19% outward). This orientation is driven by the initial anchoring of the hydrophobic end for Ch⁺, while for Ch⁻, electrostatic attraction facilitates a charged-end-first insertion. Single-particle tracking via total internal reflection fluorescence (TIRF) microscopy provided further kinetic insights: Ch⁻ aggregates adsorbed quickly and underwent dynamic redistribution, whereas Ch⁺ displayed rigid, immobilized binding once incorporated. This work unequivocally establishes molecular charge as a fundamental design parameter controlling the adsorption kinetics, binding stability, and ultimate orientation of artificial channels in lipid membranes. These findings provide essential principles for guiding the rational design of next-generation membrane-active therapeutic agents and biomimetic sensors.

2-Aryl and 2-acyl azole structural motifs widely exist in natural products, pharmaceuticals, agrochemicals and functional materials. Among various synthetic methods of 2-aryl and 2-acyl azoles, transition-metal-catalyzed direct C–H bond functionalization of azoles is more atom and step economical. A range of catalysts and reagents have been developed for the synthesis. However, tunable C2–H arylation and acylation of azoles employing the same reagent are rare and challenging. Thioesters as cheap and stable compounds are versatile building blocks in organic synthesis. They have been known to be effective arylation and acylation reagents when reacting with various organometallic reagents such as organozinc reagents, organoboron reagents, organosilicon reagents, organotin reagents, organoindium reagents, and organomanganese reagents. However, they were rarely used in C–H arylation and acylation reaction. In this paper, we report tunable C2–H aroylation and arylation of azoles with thioesters for the first time. Pd₂dba₃/P(m-tolyl)₃-catalyzed reaction of azoles with S-ethyl arylcarbothioates in dioxane at 80 °C in the presence of CuCl and tBuONa results in 2-aroylazoles. Similar reaction between benzoxazole or benzothiazole and S-dodecyl arylcarbothioates at 110 °C employing dcype as ligand affords 2-arylbenzoxazoles or 2-arylbenzothiazole. The method does not require activated thioesters, has a wide scope of substrates, good compatibility of functional groups, and controllable selectivity of acylation and arylation. Thioesters are easily prepared from the corresponding carboxylic acids. So, this protocol provides an alternative way to di(hetero)aryl ketones and di(hetero)aryl compounds bearing azoles from aromatic carboxylic acids.

Although significant advances have been accomplished in the synthesis of α-chiral carboxylic acid derivatives through Wolff rearrangement of α-diazo ketones via different asymmetric catalytic mode including transition metal/photocatalysis, chiral Lewis base/photocatalysis, chiral SPA/photocatalysis and chiral NHC/photocatalysis, to the best of our knowledge, the construction of chiral carbon-heteroatom bond through Wolff rearrangement remains underdeveloped. In this paper, the first catalytic asymmetric thia-Wolff rearrangement between α-aryl α-diazothioesters and amines has been successfully achieved under cooperative rhodium/chiral phosphoric acid catalysis, which provides efficient access to synthetically valuable chiral α-sulfenylated amide architectures. This protocol features mild reaction conditions, high efficiency, excellent stereoselectivity, a broad substrate scope, scalable synthesis and versatile product functionalization, highlighting its practical value in constructing various chiral sulfur-containing compounds. Additionally, this study significantly expand the utility of diazo compounds in Wolff rearrangement for asymmetric synthesis of sulfur-containing compounds and carbene transfer reactions.