2025-06-10 2024, Volume 42 Issue 23

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  • Comprehensive Report
    Junfeng Ding , Tianran Wang , Yan Rong , Chaoliang He , Xuesi Chen
    2024, 42(23): 2957-2969. https://doi.org/10.1002/cjoc.202400475

    Due to the immunosuppressive tumor microenvironment (TME), T cells are usually inactivated and tend to differentiate into regulatory T cells (Tregs) in the tumor tissues, which seriously hinders the anti-tumor efficiency of immunotherapy. In this study, an immune-stimulating polypeptide hydrogel conjugated with an indoleamine-2, 3-dioxygenase (IDO) inhibitor, 1-methyl- D-tryptophan (D1MT), through a glutathione (GSH)-responsive spacer was developed as an immunotherapy platform capable of regulating the TME. A combined immunotherapy system was further constructed through encapsulating doxorubicin (Dox) and immune checkpoint blocking antibody targeting programmed cell death protein 1 (aPD-1) in the hydrogel. Dox released from the hydrogel could cause the immunogenic cell death (ICD) of tumor cells and induce the maturation of antigen presenting cells (APCs). After intratumoral injection, the multiple agent-loaded hydrogel elicited effective anti-tumor immunity in mice bearing B16F10 melanoma. Moreover, compared with the control hydrogel without D1MT, the immune-stimulating hydrogel showed better efficiency in improving the immunosuppressive TME with increased number of activated T cells and reduced number of Tregs. Therefore, the immune-stimulating hydrogel has great potential as a stimuli-responsive platform for regulating suppressive TME and enhanced anti-tumor chemo-immunotherapy.

  • Comprehensive Report
    Xiaohui Liu , Hui Li , Na Xu , Yanyan Guo , Xiaoyan Zhang , Xiuli Wang
    2024, 42(23): 2970-2978. https://doi.org/10.1002/cjoc.202400642

    The conversion of aniline to nitrosobenzene (NSB), a key step in the synthesis of important chemicals, demands the development of environmentally friendly photocatalysts that operate under mild conditions. This process is driven by the need for sustainable methods, given toxic nature of aniline and its central role in the production of dyes, pharmaceuticals, and agricultural chemicals. This study reports on the synthesis of three reduced phosphomolybdate compounds with Co(II) centers and polypyridine ligands, which show great potential as photocatalysts for the mild oxidation of aniline to NSB. The synthesis uses 30% H 2O 2 as the oxidant and the compounds as the sole catalysts, achieving high conversion rates and selectivity without additional additives or photosensitizers. The integration of multidentate ligands with {P 4Mo 6} clusters significantly reduces the band gap, facilitating visible-light-driven photocatalysis. The adsorption interaction between coordinated water molecules and Co ions and H 2O 2 is found to enhance the conversion rate of aniline, a finding supported by DFT analyses.

  • Comprehensive Report
    Xu Wang , Jing Tian , Zuhao You , Le Lei , Aokang Ge , Yao Liu
    2024, 42(23): 2979-2986. https://doi.org/10.1002/cjoc.202400692

    Tin oxide (SnO 2) has been widely used as an electron transport layer (ETL) in optoelectronic devices. However, there are numerous surface or bulk defects in SnO 2, working as charge recombination centers to degrade device. Here, an electroactive and self-healing polyurethane (PHNN) was designed by integrating conjugated unit – naphthalene diimide (NDI) into a typical polyurethane backbone. Numerous hydrogen bonds and π interactions in PHNN work as non-covalent interactions to endow this polymer with superior self-healing properties. PHNN contains lots of aliphatic amine and carbonyl groups, which effectively passivate the defects in SnO 2. The π stacking of NDI units will facilitate electron delocalization, endowing PHNN with electrical activity compared with traditional polyurethane. Doping SnO 2 with PHNN can improve the conductivity and reduce the work function of SnO 2 layer, which is conducive to efficient charge extraction and transport. Using PHNN doped SnO 2 as ETL for PM6: Y6 and PM6: BTP-eC9 based inverted organic solar cells can achieve a high efficiency of 17.16% and 17.51%, respectively. Devices containing doped SnO 2 ETL show significantly improved efficiency and stability. Thus, the electroactive polyurethane doped SnO 2 interlayers show high performance interfacial modification to align energy-levels in solar cell devices, which have promising applications in organic electronics.

  • Concise Report
    Yajing Li , Jiacong Fu , Bohan Yao , Pengyu Zeng , Qiuchen Peng , Yuanyuan Li , Kai Li , Shuangquan Zang
    2024, 42(23): 2987-2992. https://doi.org/10.1002/cjoc.202400541

    Salicylaldehyde Schiff base is a kind of important photochromism system, whose photochromism process is widely acknowledged to be co-determined by the electronic structure and molecular conformation. Normally, salicylaldehyde Schiff base derivatives with α-type structures tend to exhibit photochromism while those with β-type structures tend to be photostable. However, more and more counterexamples are found, and the root cause of photochromism property of salicylaldehyde Schiff base is still unclear. In this work, a series of chiral salicylaldehyde Schiff bases and their racemates were prepared. The formers are photochromic while the latters are photostable. Influenced by Wallach’s rule, the homochiral counterparts have looser packing modes than that of the racemic counterparts. Mechanism study revealed that the pressure should be the root cause of photochromism property. Close molecule packing can restrict the photochromism property effectively after being pressed, which also explains why the photochromism of salicylaldehyde Schiff base is usually observed in solid state. This work not only reports the unique photo-responsive difference between the chiral salicylaldehyde Schiff bases and their racemates, more importantly, provides a new perspective to understand the influence of molecule pressure on their photophysical properties.

  • Concise Report
    Feiyu Qiu , Lingyun Yang , Yuan Gao , Jiapei Yang , Aiwen Lei , Wu Li
    2024, 42(23): 2993-2998. https://doi.org/10.1002/cjoc.202300644

    Deuterium labelling possesses wide applications in pharmaceuticals, chemical science and materials science. Development of efficient methodologies for the synthesis of deuterium labelled compounds, especially hydrogen isotope exchange (HIE), continued to receive an impressive attention over the years. Herein, we developed a nitrogen doped nano-scale nickel catalyst for deuterium incorporation of a variety of nitrogen heterocycles using D 2O as the isotope source. The usefulness of this approach has been demonstrated by 10 g-scale for complex pharmaceuticals. This methodology represents a practical and scalable deuteration and the air- and water-stable nanocatalyst enables efficient labelling in a straightforward manner.

  • Concise Report
    Linhui Tan , Yi Shi , Yueshan Xu , Xue Zhang , Daoxiong Wu , Zhitong Wang , Juanxiu Xiao , Huan Wen , Jing Li , Xinlong Tian , Peilin Deng
    2024, 42(23): 2999-3005. https://doi.org/10.1002/cjoc.202400591

    The direct oxidation of methane (CH 4) into high-valued C1 oxygenates production has garnered increased attention in effectively using vast CH 4 and alleviating the global energy crisis. However, due to the high cleavage energy of C—H bond and low polarity of CH 4 molecule, it is difficult to activate the first C—H bond. Furthermore, C1 oxygenates are readily inclined to be oxidized to CO 2, because their weaker C—H bond comparing with CH 4 molecule, resulting in poor selectivity. Herein, we designed ultrathin Pd xAu y alloy NWs supported on ZSM-5 (Z-5) to investigate the direct oxidation of CH 4 to high value-added oxygenate under mild conditions. By precisely adjusting the molar ratio of Pd/Au and alloying degree, Pd 9Au 1NWs/Z-5 showed an excellent yield of 11.57 mmol·g -l·h -1 and the outstanding selectivity of 95.1% for C1 oxygenates (CH 3OH, CH 3OOH and HCOOH). The  in-situ spectroscopic and mechanism analysis proved that the enhanced catalytic performance of Pd 9Au 1NWs/Z-5 was ascribed to the stable one-dimensional nanostructure and the strong synergy effect with high alloying PdAu, which could increase the adsorption capacity of CH 4 molecules on Pd atoms to promote the CH 4 conversion. This work offers valuable insights into the design concept of high-efficient catalysts and the structure-activity relationship for the direct oxidation of CH 4.

  • Concise Report
    Li-Xia Liu , Tong Niu , Yu-Qing Bai , Yong-Gui Zhou
    2024, 42(23): 3006-3012. https://doi.org/10.1002/cjoc.202400612

    Optically active phthalides are prevalent in many natural and bioactive products. Herein, a novel dynamic kinetic resolution of isobenzofuranone derivatives through palladium-catalyzed asymmetric allylic alkylation has been developed to synthesize phthalide derivatives bearing vicinal quaternary and tertiary stereocenters with high yields, showing excellent chemo-, enantio- and diastereoselectivity. Furthermore, gram-scale experiment underwent smoothly and the transformation of product could build a bridged bicyclic skeleton.

  • Concise Report
    Jie Xie , Yonghui Wang , Xiaobin Wang , Xuefeng Fang , Qinyan Zhu , Chun Cao , Ming Jin
    2024, 42(23): 3013-3022. https://doi.org/10.1002/cjoc.202400629

    Photoinitiators of the oxime ester (OXE) or ketoxime ester (OXE-CO) type can rapidly undergo N—O bond cleavage and generate free radicals to initiate photopolymerization under LED excitation, occupying an important position in the field of photocuring. However, the commercial OXEs,   e.g., OXE 01 and 02 with  λ max’s at 326 and 344 nm, respectively, still do not well match the emission spectra of LEDs. Developing novel OXEs/OXE-COs with high photosensitivity for long-wavelength LEDs has great significance. Here, four new OXEs/OXE-COs with nitro-carbazole-styrene conjugated chromophore were designed, synthesized, and used as photoinitiators. Results demonstrated that all photoinitiators had strong absorption within the UV–vis range ( λ max: 381—392 nm, ϵ max: 8200—11500 M −1·cm −1). Molecular design of the oxime ester cleavage to produce a small volume methyl group and a methacryl group with an unsaturated double bond brings high activity and low migration, respectively, in one-photon polymerization under 365—450 nm LEDs excitation. Moreover, OXEs/OXE-COs with PETA exhibited a wide processing window, high resolution (line accuracy∼100 nm) and good nano-patterning capability under 780 nm femtosecond laser irradiation in two-photon polymerization, indicating their great potential in 2D/3D microfabrication technologies.

  • Concise Report
    Hiroshige Ogawa , Yuuya Nagata , Hugh Nakamura
    2024, 42(23): 3023-3028. https://doi.org/10.1002/cjoc.202400637

    The first total synthesis of neopetromin, featuring the highly strained Tyr C-6-to-Trp N-1’ linkage, is hereby reported. This modular synthetic strategy, employing C—H arylation and Larock macrocyclization, offers a novel approach to the synthesis of various RiPPs natural product families.

  • Concise Report
    Xin Wang , Anrong Chen , Shiyin Zhao , Qiang Tao , Bo Yang , Xing Zhang , Feng Zhu
    2024, 42(23): 3029-3034. https://doi.org/10.1002/cjoc.202400651

    A highly stereoselective nickel-catalyzed cross-electrophile coupling of readily accessible, novel, stable oxygen-based glycosyl radical precursors, specifically 1, 2-glycosyl orthoesters, is developed. This approach offers an effective pathway to synthesize diverse  C-vinyl glycosides, characterized by good yields, excellent stereoselectivity, mild reaction conditions, a broad substrate scope, and versatile transformations of the resulting products.

  • Concise Report
    Gaolei Sun , Wenhui Wei , Xiaowei Zhao , Baokun Qiao , Zhiyong Jiang
    2024, 42(23): 3035-3040. https://doi.org/10.1002/cjoc.202400508

    α-Azaarene quaternary carbon centers are prevalent in drug molecules, making the development of efficient synthetic approaches of great interest. Herein, we describe an unprecedented method for constructing α-all-carbon quaternary carbon-centered azaarenes by employing photocatalytic reductive coupling of various 2, 2-disubstituted cycloproarylketones with readily available cyanoazaarenes. The reaction proceeds with high efficiency, displaying excellent compatibility with various functional groups and demonstrating high chemo- and regioselectivity. Mechanistic investigations suggest that consecutive photo-induced electron transfer (ConPET) plays a crucial role in the formation of photocatalyst with greater reducing capability, ultimately enabling the direct reductive conversion of unreactive π-bonds under mild and transition-metal-free conditions.

  • Concise Report
    Zhouying Wang , Lu Gan , Zhibin Song , Yunyun Liu , Jie-Ping Wan
    2024, 42(23): 3041-3046. https://doi.org/10.1002/cjoc.202400664

    The alkali  tert-butoxide ( tBuOK or  tBuONa) mediated generation of aryl free radical from aryl iodide remarks a milestone discovery in the free radical chemistry. However, the equivalent “alkyl halide to alkyl free radical” transformation has not yet been realized in applicable synthesis by similar catalytic tactic. In this paper, the first practical “alkyl halide to alkyl free radical” transformation mediated by  tBuOK or TMSOK in the direct α-C—H alkylation of benzoins is presented. As the parallelly significant issue as aryl free radical generation, the current work, while bringing a rather facile and useful new approach for the synthesis of diverse benzoins, represents also an important step in the alkyl free radical-based synthesis by displaying the higher generality of simple alkali base mediated radical formation.

  • Concise Report
    Yang Chen , Jingyu Zhang , Yecheng Wang , Hongguang Du , Jiaxi Xu , Zhanhui Yang
    2024, 42(23): 3047-3055. https://doi.org/10.1002/cjoc.202400265

    The reductive lactonization strategy provides an efficient access to diastereoenriched polycyclic γ-lactones. However, it is still a formidable challenge to develop an efficient and versatile protocol with excellent levels of diastereocontrol. Herein, we provide a highly diastereoselective and efficient route to diastereopure bi- and polycyclic γ-lactones, by means of an iridium-catalyzed hydride transfer strategy. This method features high levels of diastereocontrol, broad substrate scope, and high catalyst efficiency ( S/ C = up to 5000). Mechanistic studies suggest that the iridium hydride formation might be the rate-determining step, and that the hydride transfer step be the diastereo-determining step. The large steric hindrance of the iridium hydride species and intramolecular hydrogen bonding are critically key to the diastereocontrol of the hydride transfer process. From the perspectives of configurational analysis and Duniz angles of attack, the nature of diastereocontrol is well rationalized. A more general empirical rule based on facial selectivity analysis for explaining and predicting the stereochemistry is also proposed.

  • Concise Report
    Jingrong Liu , Changquan Lin , Yuan Tao , Jiang Lei , Chenyang Liao , Yanli Feng , Liangbing Fu
    2024, 42(23): 3056-3062. https://doi.org/10.1002/cjoc.202400449

    Nitrogen-containing polymers have found a wide myriad of applications in materials science and other different areas, and have attracted much attention towards the development of new synthetic methods. Ring-opening metathesis polymerization represents an area of great versatility and potential for the synthesis of highly functionalized polymers with low dispersity and control over molecular weight and architecture complexity. Expanding the scope of monomers through the incorporation of nitrogen atoms would further expand their utilities. In this work, a controlled synthesis of polymers with in-chain enamide moiety through ring-opening metathesis polymerization was developed by utilizing azetine derivatives as the monomers. Relatively short synthetic routes were designed and generated a panel of five monomers. The polymerization exhibited living characteristics, as linear relationship between molecular weights and degrees of polymerization and relatively narrow molar mass distributions were observed, which was further confirmed by successful diblock copolymers formation through sequential addition of two monomers. The resulting polymers that contain the enamide moiety within the backbone exhibited good stability and underwent facile degradation under acidic conditions.

  • Concise Report
    Wencheng Li , Wei-Yi Zhang , Baoxin Ni , Peng Shen , Yu Qiao , Xinchang Wang , Xian-Yin Ma , Wen-Bin Cai , Kun Jiang
    2024, 42(23): 3063-3068. https://doi.org/10.1002/cjoc.202400499

    Electrochemical attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) plays an important role in deciphering interfacial reaction mechanisms at molecular level. However, the corrosive etching of Si internal reflection element by OH - largely impedes reliable SEIRAS measurements in strong alkaline electrolytes. Herein, a dense and chemically inert nanocrystalline diamond (NCD) film is successfully fabricated at a thickness of ∼120 nm through hot filament chemical vapor deposition on a micromachined Si wafer to insulate the OH - etching. A reversible interfacial water feature without spectral interference of Si-O band is obtained in 1.0 mol·L -1 KOH on Au/NCD/Si film electrode. Afterwards, electrochemical CO reduction reaction on Cu film electrode is explored in different KOH concentrations ranging from 0.1 to 3.0 mol·L -1 as a model reaction. A redshift of CO L band, as well as its lower intensity but faster depletion kinetics, is noted with increasing electrolyte pH, whereas CO B is identified as an inert spectator accumulating on Cu surface. Our present work demonstrates the alkaline resistant feature of diamond/Si composite internal reflection element, which could be a powerful platform to study electrocatalytic reactions in strong alkaline media.

  • Concise Report
    Lingjuan Chen , Jiaqi Dong , Dehui Tan , Jianfeng Wu , Deng-Tao Yang
    2024, 42(23): 3069-3074. https://doi.org/10.1002/cjoc.202400512

    Construction of helicenes by inducing heteroatoms has regarded as an effective strategy to enhance the chiroptical properties. We report a facile synthesis of a multiple helicene based on four indoles with two electron-rich NBN-coved edges. The structure of the NBN-coved multiple helicene was confirmed by single-crystal X-ray diffraction analysis, revealing a twisted double [5]helicene motif with a saddle-shaped skeleton. This NBN-coved helicene showed strong green fluorescence with good photoluminescence quantum yield. Both theoretical calculations and experimental investigation have been exploited to probe the impact of electron-rich NBN units on aromaticity and photophysical properties of the helicene.

  • Concise Report
    Wanying Feng , Yuyang Bai , Jiaying Wang , Shaohui Yuan , Xiangjian Wan , Yu Chen , Bin Kan , Yongsheng Chen
    2024, 42(23): 3075-3082. https://doi.org/10.1002/cjoc.202400573

    Small-molecular organic solar cells usually exhibited unsatisfactory device stability, which might originate from their molecular diffusion behaviors. Herein, based on the all-small-molecule system HD-1:BTP-eC9, we reported a dimerized acceptor DC9, and its corresponding monomer acceptor eOD. In comparison with eOD, the dimeric acceptor DC9 displayed higher glass transition temperature ( T g) but reduced molecular planarity and crystallinity. The all-small molecule blend utilizing HD-1:eOD demonstrated a power conversion efficiency (PCE) of 15.13%, surpassing the value of 14.10% for the HD-1:DC9 blend. While, incorporating polymer donor PM6 into the HD-1:DC9 blend improved its morphology and charge transport dynamics, resulting in a device efficiency of over 16%, representing the rare case utilizing small-molecular donor and dimeric acceptor with PCE over 16%. Morphological characterization results affirmed that the surface morphologies and molecular packing behaviors of the blend films based on HD-1 were largely retained even after prolonged annealing and aging at 85 °C. Consequently, the PCEs of the blend films based on HD-1:eOD, HD-1:DC9, and HD-1:PM6:DC9 consistently remained over 98% of their initial efficiency after 1000 h of thermal annealing aging at 85 °C. These findings highlight the potential of small-molecular based active layer in the fabrication of efficient and stable OSCs.

  • Concise Report
    Chenyang Guo , Zaozao Qiu , Zuowei Xie
    2024, 42(23): 3083-3087. https://doi.org/10.1002/cjoc.202400571

    Recent advances in transition metal-catalyzed  o-carborane B—H activation have led to the rapid development of various methodologies for cage boron functionalization. For catalytic cage B—H acyloxylation, intermolecular oxygenation gave products with different regioselectivities (B(3)-, B(4)-, and B(8, 9)-selectivities). Herein, an efficient palladium-catalyzed direct cage B(4)–H oxygenation of  o-carboranylacetic acids has been achieved, where the carboxylic group serves as not only a directing group, but also a coupling partner. A wide range of substituted  o-carboranylacetic acids have been cyclized via the formation of B(4)-O bond to give the corresponding γ-lactones in modest to excellent yields. A Pd(IV) intermediate is proposed to be involved in the catalytic cycle. This work offers valuable references for the BH/OH dehydrocoupling reactions under mild conditions to produce carborane-featuring functional molecules.

  • Concise Report
    Heng Luo , Zhao-Ying Yang , Ming Zhang , Xiao-Chen Wang
    2024, 42(23): 3088-3092. https://doi.org/10.1002/cjoc.202400671

    Herein, a method for the enantioselective reduction of unprotected 2-alkylpyridines is reported for the first time. By using pinacolborane and an amide as reducing agents, a large number of 2-alkylpiperidines were synthesized with high yields and excellent enantioselectivities via a cascade process involving 1, 4-hydroboration and subsequent transfer hydrogenation. The resulting products can be easily converted to natural alkaloids.

  • Concise Report
    Meiying Huang , Zhipeng Zhou , Xin Dong , Yuyao Li , Yonghang Yang , Changye Zhan , Jiaxing Lu , Xiaoshu Wei , Yuexian Hong , Weiqi Cheng , Wei Liu , Zhongke Yuan , Xudong Chen , Zhikun Zheng
    2024, 42(23): 3093-3098. https://doi.org/10.1002/cjoc.202400552

    Chiral covalent organic frameworks (COFs) have shown promising applications in asymmetric catalysis, enantiomer separation and chiral recognition due to their tunable structures and permanent porosity. Currently, synthesis of chiral COFs mainly relies on direct- synthesis method which requires asymmetric monomers to polymerize and crystallize with symmetric monomers and post-synthesis method which has been greatly limited to having complete reactions with the micro-/meso-sized pores of COFs. Recently, the synthesis of two-dimensional COFs by covalent replacement of chiral competitor has been reported. Herein, we present the synthesis of three types of 3D COFs with tunable chirality using chiral amino acid derivative surfactant as inducer in water under ambient conditions. The hydrogen bonds and electrostatic interactions between amino acid derivative surfactant and monomers as well as their precursors facilitate the transfer of the chirality.

  • Concise Report
    You-Song Ding , Qi-Wei Chen , Jia-Qi Huang , Xiao-Fei Zhu , Zhiping Zheng
    2024, 42(23): 3099-3106. https://doi.org/10.1002/cjoc.202400600

    Many sandwich-type lanthanide complexes show extremely high energy barriers ( U eff) for the reversal of magnetization and high blocking temperatures, being the star molecules in the research area of single-molecule magnets. Herein, the preparation, structural determination, and magnetic property studies of two  ansa-bridged Er-COT (COT = cyclooctatetraenyl dianion) complexes [KDME 2][Er((η 8-COT-Si Me2) 2O)] ( 1) and [KDME 2][Er((η 8-COT-Si i Pr2) 2O)]K[Er((η 8-COT-Si i Pr2) 2O)] ( 2) were reported. The Er(III) ions in both complexes are sandwiched by two COT rings which are  ansa-bridged by a [Si-O-Si] group. Magnetic studies reveal both complexes display slow magnetic relaxations with comparable energy barriers (228(5) K for  1, and 196(4) K for  2) and blocking temperatures (10.5 K for both complexes). The difference in the relaxation times ( τ) for the two complexes was studied in details: different molecular vibrations induced by the substituents are the main reason for  τ for  1 being about 10 times longer than for  2 at the same temperature above 10 K, while the quantum tunnelling of magnetization relaxation time ( τ QTM) for  2 is about 10 times longer than for  1 below 8 K, probably owing to the different dipolar interactions. Further rearrangement of molecular network with such  ansa-bridged SMMs is promising to design molecular magnetic materials with enhanced properties or new properties.

  • Concise Report
    Xinyu Duan , Dong Cui , Mengdi Wang , Yifan Tian , Jianan Shi , Yixue Wu , Shuang Liu , Zejie Zhu , Jian Xu
    2024, 42(23): 3107-3112. https://doi.org/10.1002/cjoc.202400567

    The concurrent implementation of cascade reactions that combine biocatalysis and chemocatalysis is a challenging undertaking. Electrocatalysis provides versatile catalytic abilities and allows for mild reaction conditions, offering the potential for designing concurrent chemoenzymatic cascade reactions. The research on bioelectrocatalysis has primarily concentrated on utilizing electrocatalysis to achieve cofactor regeneration of enzymes. In contrast with previous reports, herein, we developed a deracemization strategy involving the concurrent combination of biocatalytic reduction and anodic oxidation in an undivided cell to achieve chiral sulfoxides, demonstrating the good compatibility. We anticipate this study will offer an alternative pathway for the design of the cascade reaction combined with electrocatalysis and biocatalysis.

  • Concise Report
    Xiaoting Sun , Tiantian Lu , Jialei Chen , Youzeng Li , Shan Chen , Xuelong Liao , Ying Liu , Runyu Lv , Huan Wang
    2024, 42(23): 3113-3121. https://doi.org/10.1002/cjoc.202400455

    Carbon-based nanomaterials show great potential in selective electrochemical oxygen reduction reaction (ORR) through two-electron (2e -) pathway for H 2O 2 production, which provides an eco-friendly alternative to industrial energy-intensive anthraquinone process. However, it still remains challenging to directly construct topological defects, which makes it difficult to study the working mechanism on 2e - ORR. Herein, we propose a precursor-mediated chemical vapor deposition (CVD) approach for direct growth of topological defect-rich hierarchical nanocarbons. Boric acid (H 3BO 3) is introduced into the precursor for disturbing the nucleation and growth through decomposing B-containing species, which can  in situ induce the formation of pentagon defects. The topological defect is found to be capable of introducing lattice strain, which can modify the electronic structure of nanocarbons and promote the key intermediate (*OOH) formation, thus greatly enhancing the 2e - ORR performance. Experimentally, the 2e - ORR selectivity shows a positive correlation to the topological defect density, where the average H 2O 2 selectivity reaches above 90% over a wide potential range with optimized concentration of H 3BO 3 as mediator. Moreover, in a flow cell, the hierarchical nanocarbons achieve a high H 2O 2 production rate of 998 mmol·g catalyst -1·h -1 over 20 h of continuous electrocatalysis with stable current density (>100 mA·cm -2) and Faradaic efficiency (> 90%). This work provides a straightforward method for the synthesis of active metal-free carbon-based catalyst for sustainable H 2O 2 production.

  • Concise Report
    Linjie Wei , Yi Liu , Tian Yang , Hao Rong , Xianmei Zhao , Jingtian Zhang , Junhua Luo , Zhihua Sun
    2024, 42(23): 3122-3128. https://doi.org/10.1002/cjoc.202400529

    Optical controlling of solid-sate electric properties is emerging as a non-contact and nondestructive avenue to optimize the physical properties of electronic and optoelectronic devices. In term of strong light-material coupling, two-dimensional (2D) double perovskites hold great prospects to create photo-dielectric activities for high-performance device applications. Here, we have achieved the photo-excited switching and enhancement of dielectric properties in the orientational thin films of a 2D double perovskite, (C 4H 12N) 4AgBiI 8 ( 1, where C 4H 9NH 3 + is isobutylammonium). It undergoes a structural phase transition at 384 K ( T c), triggered by the dynamic ordering of organic cations and tilting motion of isometallic perovskite sheets. Most notably, the orientational thin films of  1 are extremely sensitive to light illumination, of which the dielectric constants can be facilely photo-switched between the low- and high-states. During this photo-switching process, the dielectric constants are enhanced with a magnitude up to ∼350% under 405 nm, far beyond most of the inorganic phase transition counterparts. In addition, this photo-excited switching and enhancement of dielectric response exhibits an operational stability with superior anti-fatigue characteristics. Our work opens up a potential avenue for assembling high-performance optoelectronic devices with the controllable physical properties.

  • Concise Report
    Qing Shen , Xiaoyan Peng , Jiahong Sui , Min Peng , Xiangwei Liu , Hezhong Jiang , Rui Tan , Min Zhou , Jiahong Li
    2024, 42(23): 3129-3134. https://doi.org/10.1002/cjoc.202400530

    A visible-light-induced and efficient one-pot synthesis of  β-hydroxysulfides from olefins, thiosulfonates and HCOOCs using an EDA complex strategy under air atmosphere at room temperature has been disclosed. A plausible radical involved mechanism is proposed. During the reaction process, formates play a crucial role: first, as donors in the EDA complex; second, as providers of the hydrogen source; and third, by generating CO 2 •- to reduce peroxide intermediates, leading to the formation of  β-hydroxysulfides. In contrast to the previously reported thiol-oxygen co-oxidation reactions, this simple and sustainable approach features mild reaction conditions, operational simplicity, odorless and excellent functional group tolerance.

  • Recent Advances
    Peng Wang , Zhao-Lin He , Zi-Fei Xia , Jun Wei , Xiu-Qin Dong
    2024, 42(23): 3135-3156. https://doi.org/10.1002/cjoc.202400352

    Comprehensive Summary: Transition metal-catalyzed asymmetric hydrogenation is an efficient and direct synthetic method to access chiral compounds, which features simplicity, easy working-up process, and high atomic economy. It typically relies on precious transition metal catalytic systems, including ruthenium, rhodium, iridium and palladium, which always face the difficulties of limited resources, high cost, and environmental contamination. Therefore, great efforts were made to apply earth-abundant, low (non-)toxic, and environmentally friendly transition metals, such as iron, cobalt, nickel and copper, to the asymmetric hydrogenation in the past decades, and some considerable breakthroughs have been obtained. In this review, we mainly summarized some recent research progress of nickel-catalyzed asymmetric hydrogenation of prochiral unsaturated molecules, including olefins, imines and ketones. And continuous development of chiral nickel catalytic systems and the application of them into challenging asymmetric hydrogenation is prospected in the future.

    Key Scientists: Transition metal-catalyzed asymmetric hydrogenation has been regarded as an important and direct approach to access chiral molecules. The first example of homogeneous catalytic asymmetric hydrogenation was developed by Knowles and Horner in 1968, respectively. In 1971, Kagan developed privileged chiral DIOP ligand for asymmetric hydrogenation. Halpern and Brown made deep studies on the Rh-catalyzed asymmetric hydrogenation in 1977, respectively. Noyori developed a powerful and privileged chiral BINAP ligand in 1980. Owing to Knowles and Noyori’s great contribution in the field of catalytic asymmetric hydrogenation, they were awarded the Nobel Prize in Chemistry in 2001. In 1984, Ohkubo developed pioneering earth-abundant transition metal Ni-catalyzed asymmetric hydrogenation of ethyl α-methylcrotonate. A great many scientists made tremendous contribution to the development of chiral privileged ligands, such as, Bosnich, Kumada, Giongo, Takaya, Miyashima, Achiwa, Burk, Pflaltz, Chan, X. Zhang, Imamoto, Zhou, Genet, Sannicolo, Ding, Hoge, W. Zhang, Z. Zhang, Tang, these ligands owned wide application in the catalytic asymmetric hydrogenation. In addition, Zhou, Fan made deep investigation on the asymmetric hydrogenation of challenging aromatic heterocyclic compounds. Owing to the great importance of the development of the asymmetric (transfer) hydrogenation promoted by cheap transition metal catalytic systems, some researchers, such as Hamada, Gao, J. S. Zhou, Chirik, X. Zhang, Y.-G. Zhou, W. Zhang, Lv, Dong, Fu, Deng, and Hou, made great efforts to the development of earth-abundant nickel-catalyzed asymmetric hydrogenation of prochiral unsaturated molecules, including olefins, imines and ketones. In addition, there are some other scientists that have also made great contribution to the development of catalytic asymmetric hydrogenation and Ni-catalyzed asymmetric transformation, with too limited space to list all of them.

  • Recent Advances
    Yifei Geng , Tengfei Li , Zhenzhen Zhang , Yuze Lin
    2024, 42(23): 3157-3168. https://doi.org/10.1002/cjoc.202400543

    Comprehensive Summary: With the continuous development of photovoltaic materials, organic solar cells (OSCs) have made remarkable advancements, surpassing a power conversion efficiency (PCE) of 20%. However, the PCEs of OSCs remain lower than that of inorganic solar cells due to significant energy losses, mainly stemming from the relatively large non-radiative recombination losses (usually be expressed as ΔE3), resulting in low open-circuit voltages. This can be achieved by reducing non-radiative recombination, and hereby increasing the electroluminescence quantum efficiency (EQEEL) of the photo-active layer. This review analyzes the significance of luminescence efficiency in achieving high-performance OSCs by examining the reciprocal relationship between ΔE3 and EQEEL. High-efficiency organic solar cells can also be used as effective organic light-emitting diodes (OLEDs). The discussion provides insights into the influencing factors of EQEEL and the mechanisms for adjusting various parameters, which include enhancements in photoluminescence quantum yield and the proportion of radiative excitons. The objective is to offer insights into the crucial role of luminescence performance in OSC development, guiding researchers toward developing novel photovoltaic materials or optimization strategies to enhance the luminescence performance of the active layer in OSCs, fostering the simultaneous advancement of OSCs and OLEDs.