The treatment of poly(monohydro)silane with the zero-valent nickel precursor Ni(cod)₂ (cod = 1,5-cyclooctadiene) in toluene at 100 °C leads to the formation of a heterogeneous Ni/Si catalyst that efficiently mediates the hydrogenation of various arenes and heteroarenes under reaction conditions that are relatively mild compared to conventional heterogeneous nickel-based catalysts such as Raney nickel. For instance, the hydrogenation of benzene proceeds smoothly under 8 atm of H₂ (100 °C, 24 h) to exclusively afford cyclohexane in a quantitative yield. An X-ray photoelectron spectroscopy (XPS) analysis revealed that the composition of this heterogeneous Ni/Si catalyst resembles that of nickel-silicide, albeit that the present catalyst exhibits a catalytic activity that is significantly superior to that of commercially available nickel-silicide. This heterogeneous Ni/Si catalyst can be recycled multiple times via simple centrifugation without any noticeable decrease in catalytic activity.

Chiral 1,2,3-triazoles have emerged as valuable structural motifs in both drug discovery and materials science. Nevertheless, the catalytic asymmetric synthesis of such frameworks remains a significant challenge, primarily due to the inherent difficulty in achieving stereo control during the rapid click reaction, as well as the limited availability of broadly applicable efficient catalytic systems. Current methodologies largely focus on the synthesis of centrally or axially chiral molecules, with relatively few reports on enantioselective Cu(I)-catalyzed azide alkyne cycloadditions for the construction of planar chiral compounds. In this work, we report an efficient and broadly applicable strategy for the enantioselective synthesis of planar chiral [2.2]paracyclophanes (PCPs) employing Cu(I)-catalyzed desymmetrization. The method affords planar chiral 1,2,3-triazoles in high yields (up to 94%) and excellent enantioselectivities (up to 99%). Notably, this protocol enables the streamline efficient construction of diverse planar chiral triazoles bearing drug-like scaffolds under mild conditions and with broad functional group tolerance. Mechanistic investigations were conducted to elucidate the reaction pathway and the origin of enantioselectivity.

The design and synthesis of high-mobility n-type organic semiconductors remain a central research imperative in organic field-effect transistor (OFET) technology. While π-extended perylenediimides (PDIs) have been extensively investigated with tunable physicochemical properties, fully ring-fused PDI derivatives remain underexplored—primarily hindered by synthetic challenges inherent to cyclizing electron-deficient aromatic cores. Herein, we report f-2PDI, a fully ring-fused PDI dimer linked via a dithienothiophen-pyrrolobenzothiadiazole (TPBT) bridge, which is obtained through Scholl cyclization mediated by ferric chloride in nitromethane. Unlike the electron-rich thiophene-benzene bridging motifs utilized in previous PDI dimers, TPBT's electron-deficient fused backbone enhances electron affinity, synergizing with the electron-accepting character of PDI moieties to fine-tune frontier molecular orbital (FMO) energy levels and strengthen intermolecular electronic coupling. Comprehensive physicochemical characterization verifies low-lying FMO energy levels, broadened absorption, a highly planar backbone conformation, and enhanced packing order with a favorable edge-on orientation. These attributes translate to exceptional OFET electron mobility of 1.51 cm²·V^–1·s^–1—two orders of magnitude greater than that of its unfused analog s-2PDI (0.012 cm²·V^–1·s^–1). This striking mobility improvement underscores the effectiveness of full ring fusion in optimizing solid-state charge transport, with particular emphasis on the utility of electron-deficient bridging units for tailoring charge transport properties.

The transition metal catalyzed dialkynylation of alkenes is an attractive strategy to access variable alkynes, which have wild applications in pharmaceuticals and materials science. While documented dialkynylation methods have focused on installing alkynyl groups at 1,1- or 1,2-positions, 1,3-dialkynylation of simple alkenes remained unexplored. Herein, we developed a palladium-catalyzed carbonylative 1,3-dialkynylation strategy that installs two alkynyl groups onto alkenes in a single step, providing efficient access to 1,6-diynes from readily available aliphatic alkenes and carbon monoxide (CO). This protocol operates under mild reaction conditions and exhibits excellent functional group tolerance (34 examples, yields up to 93%), high regioselectivity, and outstanding chemoselectivity. The design of pyridine-oxazoline (PyOx) ligands in combination with EBX reagents plays a pivotal role in modulating both regioselectivity and chemoselectivity. Moreover, the 1,3-dialkynylated products can be further transformed into various value-added compounds through downstream synthetic manipulations.

Introducing volatile solid additives into the active layer of organic solar cells (OSCs) is a widely used approach to improving power conversion efficiency (PCE). The molecular conformation of these additives plays a crucial role in determining the molecular packing behavior and phase separation of the active layer. In this study, we systematically explore the effects of three different dimensions-dibenzene derivatives solid additives—one-dimensional (1D) linear diphenylacetylene (DNE), two-dimensional (2D) planar trans-stilbene (SNE), and three-dimensional (3D) stereoscopic 1,2-diphenylethane (DLE)—on device performance. Compared to the 3D additive DLE, both 1D DNE and 2D SNE show stronger interactions with the acceptor and promote its molecular packing. However, this induces an absorption red shift that significantly lowers open-circuit voltage (V_OC). In contrast, DLE retains a higher V_OC (0.887 V) due to minimal spectral shift and mitigates the V_OC-short-circuit current density (J_SC) trade-off, thereby reaching a PCE of 19.62% in the PM6:L8-BO system. Moreover, as a non-halogenated additive processed with the green solvent toluene, DLE enables a high PCE of 19.33% in the PM6:BTP-ec9 system, highlighting its promising potential for practical applications. Our findings establish a broadly applicable framework for understanding and harnessing conformation effects in solid additives to enhance OSC efficiency.

Post-functionalization of polystyrene (PS) holds a crucial role in creating novel materials from commercially available plastics as it enables the introduction of diverse chemical groups to enhance the material's properties for advanced applications. Despite the ability to introduce various functional groups onto PS, forming C–N bonds on either aromatic ring or aliphatic chain remains a significant challenge. Herein, we present a versatile strategy for site-selective C–H hydrazination of PS plastics, enabling precise functionalization of both aromatic (sp²) and aliphatic (sp³) bonds under tunable catalytic conditions. Using FeCl₃/N-chlorosuccinimide (NCS) for electrophilic aromatic hydrazination and photoinduced TBAFeCl₄ for radical-mediated aliphatic C–H cleavage, we achieve the controlled introduction of hydrazine motifs into PS derivatives with high efficiencies. A range of styrene-based polymers, including PS, SAN, SIS, SEBS, and PMS, can be used to synthesize diverse aminated plastic materials. This method can be also applicable for selective hydrazination of PS from mixed plastic. While the functionalized materials exhibit good ability in being a compatibilizer, the subsequent functional group transformations show great potential for creating (multi)functional materials. And comparative degradation studies reveal that the aliphatic C–H hydrazination might enhance the oxidative degradation of PS materials.

The difluoromethylene-bridged cyclopropane-cyclobutane (CP-CF₂-CyBu) motif represents a novel fluorinated scaffold that fuses two privileged strained rings, cyclopropane and cyclobutene, both of which constitute valuable structural elements in medicinal chemistry. This unique bicyclic framework offers attractive opportunities for expanding fluorinated chemical space in pharmaceutical design, particularly as compact, three-dimensional bioisosteres capable of enhancing metabolic stability and conferring conformational restriction. However, practical synthetic routes to access these strained bicyclic scaffolds remain underdeveloped. Herein, we report an efficient and operationally straightforward method for the diastereoselective synthesis of the CP-CF₂-CyBu scaffold through copper-catalyzed hydrodifluoroalkylation of cyclopropenes, employing 2-(difluoromethylene)cyclobutyl sulfonium salt (CB-DFAS) as the key fluoroalkylating reagent. This reagent is readily prepared in multigram quantities via a concise three-step synthesis. The protocol proceeds through in situ generated copper hydride species, involving CuH-mediated hydrocupration followed by oxidative addition, thereby delivering diverse CP-CF₂-CyBu products with high efficiency and diastereoselectivity under mild conditions. Notably, the reaction exhibits ligand-dependent stereodivergence: 1,1-disubstituted cyclopropenes with triphenylphosphine afford syn-diastereomers preferentially via a chelation-controlled transition state, whereas 1,2-disubstituted cyclopropenes with a bulky N-heterocyclic carbene ligand (L8) furnish anti-diastereomers selectively through non-chelation pathway governed by cage strain effect. Both pathways achieve high diastereoselectivities (up to >20 : 1 dr) and exhibit broad functional group tolerance, accommodating sensitive motifs including boronates, nitriles, halides, and nitro groups that remain compatible for downstream elaboration. The synthetic utility of this method is demonstrated by diverse transformations of the CP-CF₂-CyBu products, including hydrogenation, reduction, and dihydroxylation, thereby providing streamlined access to complex, medicinally relevant fluorinated bicyclic frameworks previously inaccessible via conventional synthetic strategies. This work establishes a practical platform for expanding fluorinated chemical space in drug discovery.

Adhesive hydrogels have shown great application potential in fields like biological medicine, catalyst, optical material, sensing, and analytical science. Up to now, cyclodextrin and cucurbituril are the most used macrocycles in adhesive hydrogels. However, CD/CB-based adhesive hydrogel lacks multisubstrate adhesion to some extent. Although water-soluble cationic pillararenes exhibit broad recognition capabilities toward diverse guest molecules and excellent water solubility and adhesiveness, their application in hydrogel field has rarely been reported due to the low synthetic yields and difficult purification of olefin-functionalized derivatives. Herein, water-soluble cationic pillar[5]arene (WP5) and guest molecules bearing olefin groups were combined via host-guest interactions to form supramolecular monomer, which was utilized to construct pillararene-based supramolecular hydrogels. The resulting hydrogel exhibited excellent mechanical properties with fracture elongation exceeding 1000%. Simultaneously, they demonstrated tunable self-adhesive strength and displayed adhesion to diverse substrate materials. Leveraging this adhesion capability, modular hydrogel robots were constructed from the pillararene-based supramolecular hydrogels, showing loading and transporting behaviors.

Strategies involving N–H functionalization of secondary amide and amide-bond formation have been proven to be ineffective for synthesizing N-CF₂H amides. Subjection of the N-CF₂H carbamoyl fluorides with Grignard reagents was useless to prepare N-CF₂H amide with amino acid at the carbon terminal. The biosynthesis and preparation processes of complex amide molecules often involve organic carboxylic acids. To date, abundant carboxylic acids have not been fully utilized to prepare N-CF₂H amide. Therefore, there is an urgent need to develop new strategies using organic carboxylic acids as starting materials to unlock diverse N-CF₂H amides, especially amino acid-derived amide (peptide) skeleton. Here, we report a general strategy for synthesizing N-CF₂H amide (peptide) from carboxylic acids (amino acids) as starting materials: N-thioformyl amide was prepared through known approaches, then achieving efficient desulfurization-fluorination in the presence of silver(II) fluoride. This racemization/epimerization-free approach provides access to a wide range of different N-CF₂H amides, including amino acid-derived amides (fourteen), polypeptides (three) and drug molecules (nine). Therefore, we propose an N-difluoromethylation modification of complex amide skeleton: preparation of carboxylic acids via amide decomposition or according to mature routes; synthesis of N-thioformyl amide; rapid desulfurization-fluorination.

The hydrosilylation of unfunctionalized 1,3-enynes with tertiary alkoxysilanes poses significant challenges in regulating regioselectivity and stereoselectivity. In this study, we achieved highly efficient hydrosilylation of unfunctionalized 1,3-enynes with tertiary alkoxysilanes using a cobalt catalyst supported by a cyclopropane-fused bisphosphine ligand. Specifically, arylphosphine ligands enabled highly selective cis-α-hydrosilylation of aryl-substituted 1,3-enynes (yields up to 95%, regioselectivity > 95 : 5); in contrast, cyclohexylphosphine ligands promoted cis-β-hydrosilylation of alkyl-substituted 1,3-enynes (yields up to 99%, regioselectivity > 95:5). This protocol exhibits excellent functional group tolerance and can be readily scaled up to the gram scale, thus enabling the efficient synthesis of a series of structurally novel conjugated alkenylalkoxysilanes. The resulting products can be efficiently converted into organosilicon material precursors, laying a new material foundation for the development of advanced functional organosilicon materials. Mechanistic investigations reveal that the reaction is initiated by substrate activation via a Co(0) active species, proceeds through a two-electron redox cycle, and accomplishes hydrosilylation via ligand-to-ligand hydrogen transfer (LLHT). Specifically, arylphosphine ligands modulate regioselectivity through π-π stacking interactions with the aryl moiety of enyne substrates, whereas cyclohexylphosphine ligands dictate regioselectivity via abundant van der Waals interactions with alkyl-substituted 1,3-enynes, coupled with the higher polarizability of cobalt-hydrogen bonds.

Radioiodine poses severe long-term risks owing to its persistence and bioaccumulation in aquatic ecosystems, yet the rapid removal of triiodide (I₃^–), the most stable iodine species in water, remains a fundamental challenge. Here, we report JUC-725@K⁺, a two-dimensional K⁺-coordinated crown-ether covalent organic framework (COF), in which the ordered confinement of K⁺ within the crown-ether domains markedly enhances the framework's affinity for ultrafast I₃^– capture. Driven by the synergistic effects of ion fixation, solvation suppression, and enhanced binding energy, JUC-725@K⁺ achieves 99% I₃^– removal within 6 min, with an exceptional apparent adsorption rate constant of 16.5 g·g^–1·min^–1, outperforming all previously reported porous iodine adsorbents. High removal efficiency above 97% is maintained under continuous-flow conditions, highlighting the robustness of the material. Meanwhile, K⁺ incorporation greatly improves interfacial hydrophilicity, accelerating aqueous mass transport. Density functional theory further confirms that K⁺ confinement strengthens I₃^– binding in the parent COF, establishing an ion-cooperative host-guest chemistry for scalable radioiodine capture.

Organic phototransistors hold great promise for information optoelectronics due to their tunable molecular structures, inherent flexibility, and solution processability. However, their photoresponse speed is usually constrained by the high exciton binding energy and low carrier mobility of organic semiconductors. Here, we propose a simple and effective polar molecule doping strategy to tune the dielectric constant and photoresponse speed of organic semiconductors. By introducing polar small molecules, TPBi, into the polymer semiconductor PDVT-10, the exciton binding energy is reduced through the dielectric screening effect, facilitating faster exciton dissociation. As a result, the doped organic phototransistors exhibit a remarkable reduction in photoresponse time from seconds to milliseconds while maintaining stable electrical performance. Furthermore, by integrating phototransistors with distinct response speeds, a programmable array is designed to achieve a dynamic anti-counterfeiting application. This study presents a facile, universal, and scalable approach for tuning the photoresponse speed of organic semiconductors, offering new insights and design guidelines for high-performance organic phototransistors and optical anti-counterfeiting technologies.

The flourishing development of photocatalysis offers new opportunity for the diversified conversions of organic azides. Herein, the olefinic C–H amidation of enamines with sulfonyl azides is achieved to access 1,2-enediamine derivatives in a mild, efficient, and stereo-selective manner under visible light photocatalysis. A combined experimental and computational study suggests a photocatalytic triplet-triplet energy transfer (EnT) mediated radical chain mechanistic scenario for this reaction, which is unprecedented for the conversion of sulfonyl azides to realize C(sp²)–H amidation reactions. The substrate of β-enamino esters could undergo excitation via triplet-triplet EnT process to reach the excited state, from which the homolytic cleavage of the N–H moiety could follow to initiate an H-atom transfer (HAT) event with sulfonylazides. Thus, two key radicals, α-imino C-radical and sulfonamidyl N-radical, derived from β-enamino esters and sulfonylazides, respectively, could be produced in a photocatalytic loop. Subsequently, the formed sulfonamidyl N-radical may attack the alkenyl moiety of enamines and eventually lead to the desired C–H amidation product and regenerate the key chain-propagating sulfonamidyl N-radical. In addition, the stereo-selectivity of the desired 1,2-enediamines could be tuned to exclusively give the E-isomers under photocatalytic conditions, in which the critical roles of H-bonding interactions in the presence of formic acid are revealed.

The transfer hydrogenative cross-coupling of primary alcohols and alkenes offers a streamlined and atom-economical approach to ketone synthesis, employing readily available alcohols as latent acyl equivalents and thereby avoiding the use of preactivated acylating reagents or discrete oxidation–reduction steps. Despite significant advances, existing methodologies are largely dominated by precious metal catalysis, often require elevated temperatures, and typically exhibit a strong bias toward nucleophilic alkenes, delivering branched ketone products with limited control over regioselectivity. These limitations underscore the need for complementary catalytic strategies that operate under milder conditions while expanding alkene scope and selectivity profiles. Herein, we report a dual photo- and cobalt-catalyzed transfer hydrogenative coupling of primary alcohols with alkenes, enabled by the synergistic combination of a decatungstate photocatalyst and a cobalt co-catalyst. This protocol proceeds efficiently under mild conditions and exhibits a distinct preference for electrophilic alkenes, providing linear aryl alkyl ketones with excellent regioselectivity. The transformation accommodates a wide range of aryl methanols and alkenes, demonstrating broad substrate scope and high functional group tolerance. Notably, it is readily scalable without loss of efficiency, underscoring the practicality of the transformation. Moreover, the protocol proves directly applicable to the late-stage modification of complex molecules, facilitating the concise synthesis of pharmaceutically relevant ketones and derivatives of natural products such as ibuprofen analogs and fragrance components. Preliminary mechanistic studies suggest that photoexcited decatungstate promotes hydrogen atom abstraction from aryl methanols, generating benzylic radicals that are further oxidized to aldehyde intermediates in cooperation with the cobalt catalyst. Subsequent hydrogen atom transfer (HAT)-initiated radical addition to electrophilic alkenes affords carbon–carbon bond formation with high linear selectivity. The cobalt catalyst is proposed to play a key role in mediating hydrogen transfer events and facilitating catalyst turnover. This dual-catalytic strategy thus provides an operationally simple platform for regioselective ketone synthesis from abundant feedstocks.

Hole-selective self-assembled monolayers (SAMs) are essential for high-efficiency conventional organic solar cells (OSCs), yet common SAMs like 4PACz often suffer from inhomogeneous coverage on transparent conductive oxide (TCO) substrates, limiting device efficiency, reproducibility, and stability. Herein, we introduce Ph-IDCz as a co-adsorbent with 4PACz to form a more uniform SAM that passivates uncovered TCO regions. Strong intermolecular interactions between Ph-IDCz and 4PACz suppress excessive self-aggregation of 4PACz, while enhancing anchoring to the ITO substrate and improving stability. The resulting Co-SAM device achieves a champion power conversion efficiency (PCE) of 20.23%, outperforming the single-4PACz device (19.43%). Moreover, it exhibits excellent thermal stability, retaining 89.5% of its initial PCE after 2,592 hours at 65 °C under N₂, compared to only 57.0% for the 4PACz reference. This Co-SAM strategy provides a new route toward stable and efficient OSCs.

Organic electrode materials offer advantages such as structural tunability and high redox reversibility. However, they still face challenges in pursuing long-term cycling stability and high operating voltage. To address these challenges, a donor-acceptor monomer (TPA-PQ) integrating phenanthrenequinone (n-type) and triphenylamine (p-type) units is synthesized, which then undergoes in-situ electropolymerization to form a bipolar cathode material pTPA-PQ for SIBs. The in-situ electropolymerization significantly enhances structural stability and cycle performances. As a result, the pTPA-PQ electrode exhibits a high average voltage of 3.15 V, as well as a remarkable energy density of 441 Wh·kg^–1. Notably, the average voltage achieved represents one of the highest values reported in bipolar organic electrode materials. More importantly, the pTPA-PQ electrode demonstrates excellent stability even after 10,000 cycles in a half-cell, with an average capacity decay rate of only 0.0032% per cycle. Furthermore, symmetric all-organic full cells based on pTPA-PQ achieve a high energy density of 173.8 Wh·kg^–1 and maintain stable cycling over 2,000 cycles even at a high C-rate of 6 C. This work provides a feasible pathway for developing high-performance organic electrode materials for sodium-ion batteries.

Allylic scaffolds are prevalent in natural products and bioactive molecules. The direct functionalization of inert C–H bonds at allylic position provides an ideal alternative to access functionalized allylic substructures with diverse coupling partners with step- and atom-economy. In particular, visible-light catalyzed direct functionalizations of allylic C–H bonds have emerged as a versatile platform for transforming C–H bond to carbon-carbon and carbon-heteroatom bonds with the control of chemo-, regio-, and enantioselectivity control under mild conditions. Significant progress on this topic has been achieved through different mechanistic paradigms, including photoactivation of organo-transition metal intermediates, hydrogen atom transfer (HAT), single-electron transfer (SET), electron donor–acceptor (EDA) complex excitation, radical addition as well as combining photoredox with other catalytic methods. Taken together, this review focuses on the development of C–H functionalization by visible-light catalysis with an emphasis on reaction development and mechanistic considerations. Moreover, further challenges and future efforts for this area are also discussed.