2025-12-01 2025, Volume 43 Issue 23

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  • Comprehensive Report
    Yimin Sun, Jiali Luo, Shaodan Cai, Chao Deng, Qilin Peng, Yongqiang Shi, Hongxiang Li, Jianhua Chen, Junqiao Ding
    2025, 43(23): 3065-3074. https://doi.org/10.1002/cjoc.70198

    The combination of mechanical and electrical properties in organic mixed ion-electron conductors (OMIECs) is crucial for their application in flexible, stretchable organic electrochemical transistors (OECT) intended for biological use. However, research on the simultaneous regulation of both the mechanical and electrical properties of OMIECs remains limited. In this work, poly[indacenodithiophene-alt-3,3'-dimethoxy-2,2'-bithiophene] (IDT-OTOT) based polymers were designed to finetune the balance between their mechanical and electrical properties by varying the ratios of ethylene glycol to alkyl side chains (from 100% to 50%). Our findings indicate that when the ratio of ethylene glycol to alkyl side chains was reduced to 80%, the resulting polymer P80-gIDT-OTOT exhibited superior stretchability as well as an enhanced product of the charge carrier mobility and volumetric capacitance (μC*), along with improved device stability compared to other counterparts. The OECTs utilizing P80-gIDT-OTOT demonstrated outstanding performance and remarkable stability. Furthermore, OECTs constructed with stretched P80-gIDT-OTOT exhibited strain-independent characteristics within a stretching range of 10–50%, highlighting its excellent mechanical properties. This work establishes a structure-property relationship between side chains and the mechanical and electrical properties of OMIECs, which will be beneficial for advancing next-generation flexible and wearable bioelectronics.

  • Comprehensive Report
    Hui Peng, Kaifa Dong, Xin Wang, Danyang Wang, Ying Tang, Yue Li, Guofu Ma, Ziqiang Lei
    2025, 43(23): 3075-3084. https://doi.org/10.1002/cjoc.70213

    Aqueous Zn ion capacitors (AZICs) have the features of low-cost, safety, sustainability and high energy density compared to other mainstream energy storage devices. However, the inevitable dendrite growth and side reactions severely limit the cycle life. Herein, the highly polar organic molecule triethylamine (TEA) is employed as a multifunctional electrolyte additive to enhance the stability of the Zn anode. The highly electronegative tertiary amine nitrogen within the TEA molecule preferentially coordinates with Zn ions (Zn2+), reorganizing the solvated sheath structure and reconfiguring the hydrogen bonding network. In addition, theoretical calculations and experimental results show that TEA can effectively mitigate the parasitic reaction triggered by water activity by spontaneously adsorbing on the Zn surface to form a self-assembled interfacial shielding layer, which inhibits the construction of micro electric field and the evolution of Zn dendrites. The Zn//Zn cell based on ZnSO4+TEA electrolyte achieves 3,900 h of stable cycling at 2 mA·cm–2, a more than 19-fold improvement over the ZnSO4 electrolyte (less than 200 h). Moreover, AZIC assembled with the ZnSO4+TEA electrolyte maintains 80% capacity retention and nearly 100% Coulombic efficiency after 30,000 cycles at a high current density of 4 A·g–1.

  • Comprehensive Report
    Han Luo, Liping Fang, Ying Wu, Yuangong Zhang, Feng Liu, Xinran Wang, Libin Bai, Xin Wen, Xinwu Ba, Weiping Chen
    2025, 43(23): 3085-3092. https://doi.org/10.1002/cjoc.70225

    Development of highly efficient organic photocatalysts (OPCs) is imperative in the advancement of photoinduced atom transfer radical polymerization (photoATRP). Herein, we reported a class of OPCs consisting of (difluoro)quinoxaline acceptor units, and diphenylamine donor unit. Ultrafast femtosecond transient absorption (fs-TA) spectroscopy revealed that the photoexcited OPCs formed charge-transfer triplet (3CT) states via intersystem crossing. Well-controlled photoATRP was developed by using sub-ppm (parts per million molar ratio relatives to monomer) level of these OPCs. Furthermore, the photoATRP in sealed vials were tolerant towards a substantial amount of molecular oxygen, exhibiting accelerated polymerization rate after an inhibition period. Mechanistic study elucidated that two kinds of reactive oxygen species, superoxide (O2·−) and singlet oxygen (1O2), were concurrently generated by photoinduced electron transfer and energy transfer, respectively, from the 3CT state of OPCs. The oxygen in the reaction system was consumed via the reaction of oxidize solvent by 1O2.

  • Comprehensive Report
    Hong Chen, Minghui Zhang, Ziyu Cui, Guiyi Yang, Jingwen Chen, Zonghang Liu, Yifan Wang, Huilin Xie, Haoran Lin, Xiuze Hei, Jianquan Zhang, Ben Zhong Tang
    2025, 43(23): 3093-3101. https://doi.org/10.1002/cjoc.70223

    Hot exciton organic scintillators, a class of materials that utilize triplet excitons through high-energy reverse intersystem crossing (hRISC), have attracted significant attention due to their high exciton utilization efficiency and ultrafast fluorescence lifetime. However, the limited X-ray absorption capacity of organic molecules has restricted the diversity of organic scintillators exhibiting high radioluminescence intensity. In this study, we demonstrate strong scintillation emission by constructing a simple D-A architecture with heavy- atom modification on the donor periphery, while emphasizing the critical balance between photoluminescence quantum yield (PLQY) and X-ray absorption capability. Notably, the crystalline powder of 4-(benzo[c][1,2,5]thiadiazol-4-yl)-N,N-bis(4-bromophenyl)aniline (BT-TPA-2Br) achieves a maximum radioluminescence intensity 8.76 times that of anthracene and 1.75 times that of BGO (relative light yield of ∼33460 MeV−1.), along with a rapid decay lifetime of 5.37 ns. This work provides a straightforward molecular design strategy for developing hot exciton organic scintillators that simultaneously possess good solubility, crystallinity, and high radioluminescence intensity.

  • Comprehensive Report
    Tong Lei, Hui-Min Zhu, Min Zhang, Zhi-Xin Liao, Jia-Chen Xiang, An-Xin Wu
    2025, 43(23): 3102-3108. https://doi.org/10.1002/cjoc.70236

    Structurally novel spiro-fused hexacycles, containing three indole-related structural domains: indolinone, indoline and indole, have been created by a sequential annulation of arylamine and styrylglyoxal. Up to five chemical bonds and three densely arranged rings are concurrently forged in this one-step protocol. Copper-catalyzed aerobic oxidation proceeds mechanistically through the entire domino sequence, incorporating an unusual radical-polar crossover between the styrene and arylamine. Spiro-indene-indolin-3-one motifs are selectively obtained by simple manipulation of the substitution pattern of styrylglyoxal.

  • Comprehensive Report
    Jing Zhang, Meiling Sun, Yingnan Jiang, Yuwen Su, Tong Zhao, Qing Lu, Guangchao Yin
    2025, 43(23): 3109-3118. https://doi.org/10.1002/cjoc.70265

    Designing bifunctional electrocatalysts with high activity, durability and low-cost is a top priority to advance the hydrogen energy industry. Herein, self-supported Fe-doped Ni3S2/NiPx heterojunction electrocatalysts were synthesized via a simple hydrothermal and phosphorylated method. Benefiting from the unique nanowire morphology, abundant heterojunction interface and optimized electronic structure, it requires only low overpotentials of 263 and 173 mV at 100 mA·cm–2 current density to achieve oxygen evolution reaction and hydrogen evolution reaction in 1 M KOH solution, respectively, with excellent stability of 300 and 150 h. In addition, in situ Raman and in situ EIS demonstrated that Fe doping accelerated the surface remodeling of the catalysts, enhanced electron transport efficiency, thereby enhancing the activity and stability. Remarkably, Fe-doped Ni3S2/NiPx electrocatalysts are assembled as both anode and cathode to achieve a current density of 100 mA·cm–2 in 1 M KOH and simulated seawater solution by requiring only low cell voltages of 1.517 and 1.561 V, and the loss is negligible in the 200 h endurance test. DEMS signals and density functional theory further demonstrate the intrinsic mechanism of the catalysts, doping engineering and heterogeneous interfaces can effectively reduce the energy barrier of rate-determining step and accelerate catalytic overall water splitting.

  • Comprehensive Report
    Yuanfang Wang, Junlong Tang, Wanqing Wu, Huanfeng Jiang
    2025, 43(23): 3119-3124. https://doi.org/10.1002/cjoc.70274

    Herein, it is reported that a palladium/bidentate amine ligand cooperative catalytic system has been developed to achieve the intramolecular cyclization of 1,6-enyne coupled with a Suzuki cross-coupling reaction, successfully constructing a diaryl-substituted γ-butyrolactam skeleton. The tandem catalytic mechanism significantly enhances synthetic efficiency by circumventing the isolation and purification of intermediates required in traditional stepwise synthesis, demonstrating exceptional step economy. This method provides a novel modular strategy for the rapid assembly of bioactive diaryl-containing lactam compound libraries.

  • Comprehensive Report
    Weijie Zhu, Yujuan Zhou, Bohan Zhao, Xiaolong Deng, Errui Li, Ning Liu, Kecheng Jie
    2025, 43(23): 3125-3132. https://doi.org/10.1002/cjoc.70275

    Modulating the photophysical of organic solid-state functional materials is crucial for advancing supramolecular chemistry and materials science. Here, we present a π-conjugation enhanced charge-transfer strategy to turn on the photothermal conversion properties of crown ether cocrystals. Three crown ethers (H1, H2, and H3) bearing different π-conjugated moieties are synthesized, exhibiting enhanced solid-state luminescence upon increasing molecular conjugation. In addition, three sets of host–guest cocrystals are constructed via charge-transfer (CT) interactions between these electron-rich crown ethers and electron-deficient 1,2,4,5-tetracyanobenzene (TCNB). Based on the variations in CT interactions, the resulting cocrystals transform from primarily photoluminescent behavior to efficient photothermal conversion. Detailed structural and spectroscopic analyses reveal that the extent of π-donor/π-acceptor overlap within the cocrystals is the dominant factor governing their tunable photophysical properties.

  • Comprehensive Report
    Chuan Yan, Min Wang, Jing Fang, Si Liu, Weinan Chen, Xuefeng Lu, Gang Zhou
    2025, 43(23): 3133-3141. https://doi.org/10.1002/cjoc.70269

    Tris(2,4,6-trichlorophenyl)methyl (TTM) radical oligomers with different number of spin centers are designed and successfully synthesized through C–N/C–C coupling reaction using the diphenylamine group as building block. The strong intramolecular charge transfer (ICT) interactions endow radical oligomers with obvious absorption and emission bands in near-infrared regions. Impressively, the strong electron-deficient property of TTM core and single bond linking mode between the adjacent diphenylamine spacers greatly contribute to the formation of intramolecular isolated redox centers. Accordingly, after the treatment of chemical equivalent NO•SbF6 oxidant, polyradicals are converted directly to the corresponding highest oxidation state along with the formation of quinoidal structure cation, which can be verified by UV spectra and single crystal analysis. This study develops a facile design rule for the construction of TTM-based polyradicals and provides the reference for oxidation process and mechanism of polyradical open shell molecules with the weak electron coupling systems.

  • Comprehensive Report
    Yi Ding, Changyao Liu, Chengyu Wang, Zhiwei Fan, Shaolei Qu, Jun Zhao, Wenbin Wang, Yuanhao Wang, Tinghao Yun, Jingxi Deng, Yongming Wang, Zhaoming Zhang, Li Yang, Chunyu Wang, Xuzhou Yan
    2025, 43(23): 3142-3148. https://doi.org/10.1002/cjoc.70295

    Mechanically interlocked networks (MINs) provide a versatile platform for engineering materials that combine mechanical strength with dynamic adaptability. Their performance hinges on the constrained intramolecular motion of mechanical bonds, so the deliberate selection of capping groups is essential for tailoring properties. Herein, we develop an innovative capping strategy for mechanical bonds by employing graphene oxide (GO) as the capping unit, enabling the construction of a new class of mechanically interlocked networks (GOMINs) with enhanced mechanical performance. GOMINs benefit both from the reinforcing effect of GO as a nanofiller and its innovative use as a capping unit that creates continuous mechanical bonds, collectively improving their mechanical strength and adaptability. Compared to the non-interlocked control sample, GOMINs exhibit greater fracture strength (maximum stress: 9.4 vs. 3.6 MPa), higher toughness (22.3 vs. 9.7 MJ/m3), and increased elongation at break (359% vs. 328%). Notably, despite these significant enhancements, GOMINs maintain good energy dissipation capacity and thermomechanical stability owing to the constrained intramolecular motion of mechanical bonds. This strategy endows GOMINs with distinctive properties, providing a promising platform for the design of advanced composite materials with enhanced and tunable multifunctionality.

  • Comprehensive Report
    Qing Guo, Jiang Wu, Jiawei Ru, Xingchen Zhang, Chao Li, Erjun Zhou
    2025, 43(23): 3149-3156. https://doi.org/10.1002/cjoc.70296

    The surface charge properties and local dipole moment of terminal groups have a significant impact on molecular packing and aggregation performance of non-fullerene acceptors (NFAs) for organic solar cells (OSCs). Here, we utilize the interactions between different building blocks within the molecule to regulate the dipole asymmetry of terminal groups by introducing asymmetric inner side chains. Three NFAs, BTA80, BTA81 and BTA82 are designed and synthesized with different substitutions of benzotriazole (BTA)-based inner side chains. The asymmetric introduction of BTA-based inner side chains can modulate the asymmetric surface electrostatic potential and local dipole moments of the terminal groups through the interactions between BTA and the terminal groups, which in turn modifies the molecular orientation and enhances molecular packing. As the result, D18:BTA82-based OSCs achieve the champion power conversion efficiency (PCE) of 17.70% compared to D18:BTA80 and D18:BTA81-based devices with PCE of 16.06% and 16.65%, respectively. Moreover, by introducing the BTA82 as the third component into D18:L8-BO system, the ternary device exhibits a significant improved PCE of 19.60% compared to the device based D18:L8-BO (PCE of 18.73%). This work provides a novel insight into the design of asymmetric NFAs for high performance OSCs.

  • Concise Report
    Huan Zhang, Chenchen Ma, Fengfeng Yin, Yu Jiang, Jiaqi Du, Peifang Lu, Jianhua Wang, Jitian Liu, Xiaoxun Li
    2025, 43(23): 3157-3164. https://doi.org/10.1002/cjoc.70191

    The asymmetric construction of polycyclic spiroindolines featuring one or more quaternary stereocenters remains a significant challenge in synthetic chemistry. We report a highly chemoselective and stereoselective cascade cycloadditions of newly designed oxazepino indolones with 5-methylene-1,3-dioxanones, employing an iridium catalyst in combination with the Carreira ligand for the divergent synthesis of chiral polycyclic spiroindolines. This strategy enables the construction of a series of pentacyclic spiroindolines featuring two chiral quaternary stereocenters and one tertiary stereocenter in good yields with excellent chemoselectivity and stereocontrol (30 examples, up to 81% yield, >20 : 1 dr, 99% ee). The process was scalable, and synthetic transformations of the products were performed to demonstrate their practical utility.

  • Concise Report
    Tian-Tian Ren, Xin-Xin Yu, Yun-Tao Huang, Zhengyi Di, Cheng-Peng Li
    2025, 43(23): 3165-3170. https://doi.org/10.1002/cjoc.70209

    One-step purification of ethylene (C2H4) from acetylene/ethane/ethylene (C2H2/C2H6/C2H4) ternary mixtures remains a challenging task in the chemical industry. While hydrogen-bonded organic frameworks (HOFs) have shown promise for separating C2 hydrocarbons—typically favoring adsorption in the order of C₂H₆ > C₂H₄ > C₂H₂—existing materials have largely been limited to binary separations, particularly C₂H₄/C₂H₆. Here, we report a robust HOF material, HOF-PTBA, that selectively adsorbs both C₂H₂ and C₂H₆, enabling one-step separation of high-purity C₂H₄ from ternary C2 mixtures. HOF-PTBA exhibits the highest C₂H₆/C₂H₄ and C₂H₂/C₂H₄ adsorption ratios among all reported HOFs. Molecular simulations reveal that C₂H₂ and C₂H₆ form multiple strong interactions with the framework's pore walls, while C₂H₄ exhibits only weak interactions, allowing it to pass through unbound. HOF-PTBA also demonstrates excellent stability under humid and acidic conditions, and can be synthesized via a simple solvent evaporation process, making it scalable and cost-effective. These features highlight its strong potential for practical application in industrial gas purification.

  • Concise Report
    Xinghao Cai, Wei Lu, Chen Ma, Ying Kang, Yuqiang Ren, Xue Meng, David J. Craik, Shiming Fan, Lai Yue Chan, Shouxin Liu
    2025, 43(23): 3171-3177. https://doi.org/10.1002/cjoc.70222

    A nickel-catalyzed cascade C(sp2)–H alkynylation/hydroamination of unprotected α-substituted benzylamines is achieved using a transient directing group (TDG). The combination of a TDG with a nickel catalyst significantly improves the overall step- and atom-economy. Studies have shown that the p-trifluoromethylbenzoic acid ligand is critical for achieving C(sp2)–H alkynylation and subsequent intramolecular hydroamination. This protocol provides a straightforward and efficient route for synthesizing substituted 1H-isoindoles, featuring good substrate compatibility.

  • Concise Report
    Jiahan Li, Xiao-Yong Duan, Yuxuan Feng, Peipei Xu, Zhongyu Yang, Zhihang Li, Jing Cao, Jing Qi
    2025, 43(23): 3178-3182. https://doi.org/10.1002/cjoc.70234

    Azaspiro[4.5]decane scaffold represents a privileged structural motif that is widely found in natural products, bioactive molecules, and pharmaceuticals. Herein, we report the first N-heterocyclic carbene (NHC)-catalyzed [5+1] annulation of α,β-γ,δ-unsaturated aldehydes with 3-aminomaleimides for the efficient construction of azaspiro[4.5]decanes. This mechanistically distinct transformation proceeds under mild conditions to afford desired spirocyclic products in good yields (up to 85%) with excellent enantioselectivities (99% ee). Notably, this enantioselective catalysis demonstrates broad substrate compatibility, enabling efficient late-stage functionalization of structurally diverse pharmaceuticals and bioactive molecules.

  • Concise Report
    Ying Lei, Jiaxin Li, Yi Cheng, Chuanlan Xu, Honglin Li
    2025, 43(23): 3183-3192. https://doi.org/10.1002/cjoc.70221

    Dual-atom catalysts (DACs) show attractive prospects for the oxygen reduction reaction (ORR), yet face challenges in precise charge modulation that balances the activity and durability. Herein, we present a N,S-coordinated Fe dual atomic catalyst modified by Fe3C nanoclusters (Fe3C/Fe2NxS) through pyrolyzing the mixtures of ZIF-8-encapsulated iron dimers and sulfur-doped C3N4. Aberration-corrected STEM and synchrotron X-ray absorption spectroscopy (XAS) validated that the catalyst was composed of Fe dual atomic sites and Fe3C nanoclusters, in which Fe dual atoms were coordinated by five N atoms and one S atom. Fe3C/Fe2NxS exhibited excellent ORR activity in alkaline media, displaying a high half-wave potential (E1/2 = 0.894 V vs. RHE) with near 4e selectivity (n = 3.92) and maintaining 86.8% retention after 20000 s, superior to commercial Pt/C. Impressively, the assembled zinc-air battery delivered exceptional peak power density (163 mW·cm–2) and 200-hour robust stability. Density functional theory (DFT) calculations revealed that electron transfer from Fe of Fe2NxS to neighboring Fe3C induced local charge asymmetry, shifting the d-band center closer to Fermi level, thereby enhancing O2 activation. Moreover, the OOH* formation energy barrier was reduced to 0.52 eV in Fe3C/Fe2NxS, accelerating ORR reaction kinetics. This work establishes nanocluster-mediated electronic redistribution to tailor charge asymmetry for high-performance electrocatalysts.

  • Concise Report
    Sinuo Li, Richard J. Harrison, Wei Li, Michael A. Carpenter
    2025, 43(23): 3193-3198. https://doi.org/10.1002/cjoc.70219

    This paper investigates the structure-property relationships of three zero dimensional (0D) organic-inorganic hybrid metal halides, focusing on the influence of metal cations on their thermal and magnetic properties. Three transition metal bromides—MnBr2, FeBr3, and CuBr2—were selected to coordinate with a large organic ion, (C6H5)3PCH3+, to form 0D hybrid structures. By maintaining the organic component constant and varying the metal centres, we explore how the metal cation affects the structural characteristics, thermal and magnetic properties using differential scanning calorimetry (DSC), heat capacity measurements and magnetic measurements. The results indicate the influence of metal cations on packing styles and intermolecular interactions of 0D hybrid metal halides, which contribute to the different thermal and magnetic behaviours. Through varying metal cation, it is possible to tune properties by affecting structural characteristics, which could be significant for designing and optimizing devices and applications. In particular, the Fe-phase is multiferroic below 11 K, i.e., ferroelastic, ferroelectric and weakly ferromagnetic.

  • Concise Report
    Gang Wang, Xian Du, Zhiwen Nie, Hengzhi You, Qin Yin
    2025, 43(23): 3199-3204. https://doi.org/10.1002/cjoc.70224

    Chiral methylbenzylamines and arylbenzylamines are important structural motifs that are widely present in many bioactive compounds and drug molecules. In this study, we applied readily available ruthenium complexes, comprised of a bisphosphine and two chiral amino acid anionic ligands, in asymmetric reductive amination of benzyl ketones with ammonium salts for the first time. Excellent enantioselectivities (up to 99% ee) have been achieved by merely fine-tuning the amino acid structure, thereby decreasing the need for more expensive bisphosphine ligands. We anticipate that this new method will find broad applications in organic synthesis, especially in the preparation of chiral pharmaceutical intermediates.

  • Concise Report
    Yuying Yang, Chunyan Xing, Mengchu Feng, Yajiao Su, Qin Wang, Dianshen Pang, Xiao Feng, Yuanyuan Zhang
    2025, 43(23): 3205-3212. https://doi.org/10.1002/cjoc.70220

    Enzyme immobilization is a crucial step in advancing the industrial application of biocatalysts. Achieving effective enzyme encapsulation and precise tailoring of the enzyme microenvironment is essential for maximizing catalytic performance, yet remains a challenge. In this study, we synthesized hierarchically porous covalent organic framework (COF) aerogels, incorporating alkyl chains of varying lengths on the framework, to enable efficient enzyme immobilization, facilitate mass transfer and fine-tune the microenvironment. The introduction of alkyl chains modulated enzyme-COF interactions, inducing interfacial activation and promoting open enzyme conformation with more accessible active sites. Notably, increasing the length of alkyl chains strengthened enzyme-COF interactions, and the enzyme immobilized on the COF aerogel with the longest alkyl chains (C6) showed the highest activity and stability, achieving more than twice the conversion of the free enzyme even at low temperatures (0–20 °C) and maintaining 90% of its initial conversion after thermal treatment at 80 °C. Furthermore, COF aerogel-immobilized enzymes maintained high conversion in continuous-flow reactions for 8 h, demonstrating operational robustness. The generality of this approach is validated with multiple lipases, showing enhanced activity. This study highlights the potential of functionalized COF aerogels as a versatile and robust platform for developing high-performance biocatalysts.

  • Concise Report
    Hai-Run Yang, Xue-Qian Wei, Guan-Zhi Wang, Chen Zhao, Shi-Shuang Huang, Zhi-Gang Li, Wei Li
    2025, 43(23): 3213-3220. https://doi.org/10.1002/cjoc.70242

    Chiral hybrid metal halides (HMHs) are gaining significant attention as next-generation materials for piezoelectric energy harvesting and underwater ultrasound sensing, owing to their facile synthesis, structural tunability, and inherently low acoustic impedance. However, most chiral halide crystals lack longitudinal piezoelectricity due to centrosymmetric space group limitations, while low-dimensional chiral analogs with reduced elastic moduli remain insufficiently investigated. Herein, we report two chiral zero-dimensional HMHs compounds—R-(4MeOPEA)2SnBr6 and S-(4MeOPEA)2SnBr6 (4MeOPEA = 4-methoxy-α-methylbenzylammonium), that simultaneously exhibit remarkable longitudinal and shear piezoelectric responses. When embedded into polydimethylsiloxane (PDMS) composite matrices, these materials demonstrate high-efficiency mechanical to electrical energy conversion and robust performance in underwater acoustic detection. Notably, the dual-mode piezoelectric behavior, coupled with their intrinsically low acoustic impedance, eliminates the need for external impedance-matching layers while preserving elevated ultrasonic sensitivity. This work establishes a new paradigm for designing high-performance piezoelectric materials within HMH frameworks and broadens the scope for their deployment in advanced sensing and energy-harvesting technologies.

  • Concise Report
    Weiguo Wang, Jingyu Wang, Yanqin Wang, Zhenghu Xu
    2025, 43(23): 3221-3226. https://doi.org/10.1002/cjoc.70232

    A copper-catalyzed tandem click/amidation reaction involving various alkynes, azides, and dioxazolones has been developed for the synthesis of fully substituted 5-amide-1,2,3-triazoles. The key step in this reaction is the interception of the in situ-formed cuprate-triazole intermediate with N-acyl nitrenes, which are generated from dioxazolones. The choice of precursor for the N-acyl nitrenes plays a crucial role in the success of the reaction. This method is characterized by a broad substrate scope, mild reaction conditions, and complete regioselectivity.

  • Concise Report
    Feng Ma, Yirong Qian, Xiang Chen, Zhentao Xiao, Wang Hu, Wenxiang Yan, Bei Liu
    2025, 43(23): 3227-3234. https://doi.org/10.1002/cjoc.70238

    Controllable fabrication of multi-electroactive sites and morphology-ordered carbon electrodes with excellent capacity and alleviating self-discharge behavior for aqueous redox-enhanced supercapacitors (SCRE) is highly desirable but still challenging. Herein, the N/P/S-rich carbon nanosheets with ultrathin thickness (2–3 nm) and hierarchical porous structure are successfully prepared via phytic acid-driven interfacial phosphorization strategy using S-bridged covalent triazine framework nanosheets (CTFS) as precursor, which are synthesized through a eutectic molten salt-induced ionothermal polymerization. The carbon electrode with adequate N/P/S active sites is pioneeringly introduced in SCRE, clarifying that the coupling hierarchical porous structure and multi-electroactive sites can effectively enhance the interface interaction between carbon electrodes and redox electrolytes via the ex-situ characterizations and theoretical calculations. Consequently, the resultant N/P/S-rich carbon nanosheet (PCTFSC) enables SCRE in KI-doped H2SO4 electrolyte to achieve state-of-the-art specific capacity (1586 mA·h·g–1 at 1 A·g–1) with 60% of capacity retention at 16 A·g–1 and ultra-high energy density of 816 Wh·kg–1, exceeding the reported aqueous supercapacitors thus far. Moreover, the PCTFS based SCRE also exhibits a low self-discharge rate (holding 50% of open circuit potential after 15 h). This study provides new insights to design and regulate advanced carbon materials from the atom level and nano-morphology toward high performance SCRE.

  • Concise Report
    Zhikai Qi, Xingxing Zhao, Ke Zhang, Nan Zhang, Xian-Ming Zhang
    2025, 43(23): 3235-3242. https://doi.org/10.1002/cjoc.70235

    Organic-inorganic hybrid silver halides have emerged as promising materials for optoelectronic devices due to their unique photoluminescence (PL) properties, excellent stability, and environmental benignity. However, their PL efficiency remains limited by weak Ag+-centered radiative recombination and significant non-radiative losses. Herein, we report on a facile hydrogen-to-fluorine (H/F) substitution strategy to enhance luminescent performance in hybrid silver halides by strengthening argentophilic interactions. Using tetraethylammonium (TEA+) and its fluorinated analogue triethyl(2-fluoroethyl)ammonium (FTEA+), we synthesized two isostructural one-dimensional silver bromide hybrids: (TEA)Ag2Br3 and (FTEA)Ag2Br3. The fluorinated compound exhibits a broadband yellow-white emission with a PL quantum yield (PLQY) of 11.9%, markedly higher than the <1% PLQY of weak blue light emission for its non-fluorinated counterpart. Density functional theory calculations reveal that enhanced metal-to-metal charge transfer (MMCT) and halide-to-metal charge transfer (XMCT) processes, promoted by reduced Ag···Ag distances via F···Br interactions, are responsible for the improved PL properties. This substitution strategy was further validated in silver iodide systems, confirming its general applicability. Moreover, the excellent thermal stability and broad emission profile of (FTEA)Ag2Br3 enable its integration into white light-emitting diodes, achieving a high color rendering index of 82.7. These observations provide a new avenue for rational design of high-performance Ag-based hybrid luminescent materials.

  • Concise Report
    Wei Gao, Lang Li, Ruijie Ma, Han Liu, Ninggui Ma, Xinjing Zhao, Yang Ren, Gang Li, Zhanhua Wei
    2025, 43(23): 3243-3251. https://doi.org/10.1002/cjoc.70239

    Herein, we designed and synthesized five small molecule acceptors (SMAs), Se-1 to Se-5, by systematically varying the bifurcation sites of branched alkyl chains on selenophene[3,2-b]thiophene unit to investigate the steric hindrance effects of external alkyl chain in Y6-type SMAs on molecular stacking, active layer morphology, and photovoltaic performance. As the steric hindrance of branched alkyl chains decreased, the bandgap of SMAs narrowed with π–π stacking interactions between adjacent molecules enhanced, and the reorganization energy with D18 decreased. In particular, the strong steric hindrance from 1-position branched alkyl chain significantly suppressed π–π stacking, resulting in reduced carrier mobility within the active layer. Conversely, the weaker steric hindrance from 5-position branched alkyl chain led to excessive crystallinity of the acceptor, causing an uneven donor–acceptor distribution and imbalanced charge transport. Notably, the 2-position branched alkyl chain endowed Se-2 with optimal crystallization behavior, enabling a uniform phase distribution and balanced charge mobility. As a result, binary device based on D18/Se-2 achieved an efficiency of 19.65%, representing the highest reported efficiency for selenium-containing SMAs. This work underscores the critical role of exo-alkyl chain steric hindrance regulation, offering valuable insights for the rational design of high-performance SMAs.

  • Concise Report
    Xing Yan, Yetai Cheng, Qi Liang, Zhengdong Wei, Xingyue Cui, Yueheng Liu, Shuyue Song, Chenyi Zhang, Haishuo Guo, Huanxiang Jiang, Hao Lu, Zhishan Bo, Yahui Liu
    2025, 43(23): 3252-3258. https://doi.org/10.1002/cjoc.70241

    This study deliberately designs and synthesizes three HTMs: m-PhACz, p-PhACz, and p-DPAPCz, incorporating carbazole or diphenylamine groups linked through a benzene ring and functionalized with phosphonic acid groups. Notably, m-PhACz, featuring a carbazole unit and meta-substituted phosphonic acid, exhibits superior hole transport mobility and hydrophilicity, fostering strong intermolecular interaction with indium tin oxide. Consequently, m-PhACz-based devices achieve an outstanding power conversion efficiency of 19.44%, which is much higher than p-PhACz (18.30%) and p-DPAPCz (17.38%) based ones. Our work sets a new benchmark for high-performance OSC fabrication.

  • Concise Report
    Ruiyuan Xu, Binye Cao, Yibo Wang, Jingyi Zhang, Yuping Huang, Yihan Gao, Wanmei Li
    2025, 43(23): 3259-3265. https://doi.org/10.1002/cjoc.70244

    Current methods to access aryl/alkyl thiol-substituted bicyclo[1.1.1]pentane (BCP) derivatives (valuable bioisosteres for thiophenols/ thioethers) remain underdeveloped. Herein, we report a photocatalytic multicomponent reaction via consecutive photoinduced electron transfer (ConPET) to enable simultaneous Csp3-C and Csp3-Y (Y = S, Se, Te) bond formation on [1.1.1]pentanes. This strategy delivers diverse alkyl halides (Cl, Br, I; primary, secondary, tertiary). Late-stage derivatization of drug molecules (e.g., aspirin, methylprednisolone) and oxidations to sulfoxides/sulfones demonstrate synthetic versatility. Mechanistic studies support a radical relay pathway initiated by ConPET-mediated alkyl radical generation. The method establishes a robust platform for constructing chalcogen-rich BCP bioisosteres, addressing a critical gap in medicinal chemistry and offering significant potential for drug discovery.

  • Concise Report
    Chi Zhang, Wei Han, Li-Dan Zhang, Zhi-Liang Shen, Mengtao Ma, Xue-Qiang Chu
    2025, 43(23): 3266-3272. https://doi.org/10.1002/cjoc.70250

    Fluoroalkene and 1,2-enedichalcogenide represent two classes of valuable structures with wide applications, yet methods for their direct integration remain unknown. Herein, we report a dehalogenative 1,2-dichalcogenation reaction of internal fluoroalkyl alkenes and readily available disulfides, thiols, or diselenides for the synthesis of diverse fluoroalkenyl 1,2-enedichalcogenides. Multiple carbon-halogen bonds in perfluoroalkyl-containing alkenyl iodides can be selectively cleaved under mild and transition-metal-free conditions. This protocol features a broad substrate scope, good scalability, and the ability to modify complex molecules. Mechanistic studies revealed that the key step in the reaction is the formation of a reactive fluoroallene, which is readily attacked by nucleophilic thiolate anions to achieve an unconventional defluorinative chalcogenation.

  • Concise Report
    Yue Yu, Yuhao Jiang, Xin Jiang, Jianmin Huang, Yingming Song, Yucai Su, Jubin Liu, Hua Cao
    2025, 43(23): 3273-3280. https://doi.org/10.1002/cjoc.70247

    In this study, we outline a versatile method for the preparation of trifluoromethyl-containing unsymmetrical disulfides via catalytic photoredox difunctionalization of alkenes using symmetrical tetrasulfide (RSSSSR) and Langlois' reagent (CF₃SO₂Na). Notably, this method is also suitable for the late-stage modification of pharmaceutical molecule derivatives. Furthermore, a set of experimental investigations, such as radical trapping experiment, scrambling experiment, cyclic voltammetry (CV) measurement, Stern-Volmer analysis, on/off light-control experiments and a radical cascade experiment have been performed to support the photocatalytic reductive quenching cycle and radical-radical coupling reaction pathway.

  • Concise Report
    Shixun Guo, Wenjinyi Liu, Pan Wang, Wei Wang, Yongqiang Zhang
    2025, 43(23): 3281-3286. https://doi.org/10.1002/cjoc.70245

    Herein, we wish to report a novel photocatalytic ring opening reaction of silacyclobutanes (SCBs) with alkenes using hexafluoroisopropanol (HFIP) as the promoter. The protocol is mild and green, and is capable of accommodating a wide range of active alkenes, allowing for the facile synthesis of challenging silanols with a tetraorganosilicon stereocenter in good yields in combination with the following hydrolysis. Notably, this strategy could be extended to the reaction with ethynylbenziodoxolone.

  • Concise Report
    Bai-Lin Wang, Kehan Qian, Chuan Wang, Yan-Qi Ma, Huang-Jie Zhou, Xing-Wang Wang
    2025, 43(23): 3287-3294. https://doi.org/10.1002/cjoc.70243

    Chiral β-amino alcohols and vicinal diamine structures are undoubtedly important and ubiquitous backbones in pharmaceutical drugs and natural products. Herein, an iridium-catalyzed asymmetric cascade ring-opening/allylic amination reaction was developed between vinyl heterocyclic propanes and aromatic or aliphatic amine derivatives, which delivered optically active β-amino alcohols and vicinal diamines in good yields with excellent enantioselectivities. The reported transformations were provided with broad amino substrate scope and substituent tolerance, and the synthetic utility was also demonstrated by robust and downstream transformations. The current protocol established a practical synthetic platform for diverse optically active four carbon aliphatic amino alcohols and vicinal diamines.

  • Concise Report
    Wenlong Ren, Jinzi Huang, Jintao Ou, Yuan Shi, Yian Shi
    2025, 43(23): 3295-3301. https://doi.org/10.1002/cjoc.70248

    This work describes an effective Pd-catalyzed isomerization-hydroformylation of internal olefins with HCO2H and N-formylsaccharin, providing a wide variety of linear aldehydes in up to 72% yield with up to 18 : 1 l/b ratio. The olefin substrate can bear various functional groups. Conjugated olefins can also be efficiently isomerized and hydroformylated. The reaction is easy to operate and requires no handling of CO and H2. To the best of our knowledge, the current process represents the first example for Pd-catalyzed efficient isomerization-hydroformylation process of internal olefins to predominately give linear aldehydes.

  • Recent Advances
    Chen Liu, Renxiu Zhang, Yunge Liu, Yunfei Zhang
    2025, 43(23): 3302-3328. https://doi.org/10.1002/cjoc.70202

    The topic of C–H functionalization and C–O formation is the most important area in organic synthesis. Traditional methods are very limited due to the necessary external oxidants, whereas the rapidly developing electrochemical synthesis uses electrons as internal redox reagents. Consequently, electrochemical C–H functionalization for the construction of C–O bonds has emerged as an active area of research. This review categorizes recent reports on the electrochemical formation of C–O bonds with various C–H sources based on the hybridization (sp3, sp2) of the carbon atoms involved. Potential readers will gain a more comprehensive understanding of advances in the field through this review.