Pub Date : 2026-01-30DOI: 10.31635/ccschem.026.202506925
Yiting Wang, Kai Guo, Bixian Chen, Huiqing Yuan, Shuang Yang, Honglei Zhang, Yu Zhao, Jinzhi Yi, Long Jiang, Zhiji Han
Achieving high long-term stability is one of the primary challenges in molecular-based photocatalytic systems. Herein, we report the synthesis of two iron-alizarin pentanuclear complexes for highly durable photocatalytic CO2 reduction under visible-light irradiation. These self-sensitized molecular photocatalysts last over 360 hours without loss of activity, achieving an unprecedented turnover number of 9930 and a selectivity of 96% in CO2-to-CO conversion. The system exhibits high activity even under a low concentration of CO2. The exceptional stability of the photocatalyst is attributed to its O2-tolerant nature of the anthraquinone ligands. Substitution of the redox-inactive metal Na+ with Li+ in the cluster accelerates the formation of active intermediates and significantly improves the photocatalytic activity, as evidenced by UV–vis, fluorescence quenching, and electrochemical studies.
{"title":"Iron-Alizarin Complexes for Highly Stable Photocatalytic CO2 Reduction","authors":"Yiting Wang, Kai Guo, Bixian Chen, Huiqing Yuan, Shuang Yang, Honglei Zhang, Yu Zhao, Jinzhi Yi, Long Jiang, Zhiji Han","doi":"10.31635/ccschem.026.202506925","DOIUrl":"https://doi.org/10.31635/ccschem.026.202506925","url":null,"abstract":"Achieving high long-term stability is one of the primary challenges in molecular-based photocatalytic systems. Herein, we report the synthesis of two iron-alizarin pentanuclear complexes for highly durable photocatalytic CO<sub>2</sub> reduction under visible-light irradiation. These self-sensitized molecular photocatalysts last over 360 hours without loss of activity, achieving an unprecedented turnover number of 9930 and a selectivity of 96% in CO<sub>2</sub>-to-CO conversion. The system exhibits high activity even under a low concentration of CO<sub>2</sub>. The exceptional stability of the photocatalyst is attributed to its O<sub>2</sub>-tolerant nature of the anthraquinone ligands. Substitution of the redox-inactive metal Na<sup>+</sup> with Li<sup>+</sup> in the cluster accelerates the formation of active intermediates and significantly improves the photocatalytic activity, as evidenced by UV–vis, fluorescence quenching, and electrochemical studies.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"478 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.31635/ccschem.026.202506907
Zhuo-Min Chi, Ju-Song Yang, Liang Xiao, Wen-Hui Pu & Yong-Min LiangState Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000
CCS Chemistry, Ahead of Print. Transition metal-catalyzed hydrofunctionalization of alkynes via radical pathways has become a powerful strategy for synthesizing alkenes. However, the employment of non-halide–based electrophilic radical precursors in such transformations remains ...
{"title":"Substrate-Controlled Nickel-Catalyzed Regiodivergent Hydrocyanoalkylation of Various Alkynes with Cyclobutanone Oxime Esters","authors":"Zhuo-Min Chi, Ju-Song Yang, Liang Xiao, Wen-Hui Pu & Yong-Min LiangState Key Laboratory of Applied Organic Chemistry and College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000","doi":"10.31635/ccschem.026.202506907","DOIUrl":"https://doi.org/10.31635/ccschem.026.202506907","url":null,"abstract":"CCS Chemistry, Ahead of Print.<br/>Transition metal-catalyzed hydrofunctionalization of alkynes via radical pathways has become a powerful strategy for synthesizing alkenes. However, the employment of non-halide–based electrophilic radical precursors in such transformations remains ...","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"44 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146102023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-27DOI: 10.31635/ccschem.025.202507113
Zhisen Wei, Dong Wu, Chengmi Huang, Guoyin Yin, Yangyang Li
Substituted small spirocyclic rings represent valuable structural motifs in drug discovery. However, achieving modular and precise stereochemical control in their synthesis-particularly for heteroatom-substituted systems-remains underdeveloped. Here, we report a nickel-catalyzed divergent intramolecular arylative cyclization of unactivated alkenes tethered to carbonyl-based electrophiles, employing aryl boronic acids as coupling partners. This strategy enables complementary in situ and migratory cyclization pathways, providing access to a diverse array of heteroatom-substituted (OH, NHR) small spirocyclic frameworks with excellent regio- and trans-selectivity. The reaction features broad substrate scope, efficiently accommodating challenging internal and 1,1-disubstituted unactivated alkenes as well as a wide range of aryl boronic acids. The synthetic utility of this transformation is further demonstrated through downstream derivatizations and a concise bioisosteric modification of bioactive molecule.
{"title":"Unlocking Diverse Spirocyclic Chemical Space Enabled by Nickel Catalysis","authors":"Zhisen Wei, Dong Wu, Chengmi Huang, Guoyin Yin, Yangyang Li","doi":"10.31635/ccschem.025.202507113","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507113","url":null,"abstract":"Substituted small spirocyclic rings represent valuable structural motifs in drug discovery. However, achieving modular and precise stereochemical control in their synthesis-particularly for heteroatom-substituted systems-remains underdeveloped. Here, we report a nickel-catalyzed divergent intramolecular arylative cyclization of unactivated alkenes tethered to carbonyl-based electrophiles, employing aryl boronic acids as coupling partners. This strategy enables complementary <i>in situ</i> and migratory cyclization pathways, providing access to a diverse array of heteroatom-substituted (OH, NHR) small spirocyclic frameworks with excellent regio- and <i>trans</i>-selectivity. The reaction features broad substrate scope, efficiently accommodating challenging internal and 1,1-disubstituted unactivated alkenes as well as a wide range of aryl boronic acids. The synthetic utility of this transformation is further demonstrated through downstream derivatizations and a concise bioisosteric modification of bioactive molecule.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"93 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The practical application of lithium-sulfur (Li-S) batteries is severely hampered by the polysulfides shuttle effect and sluggish redox kinetics. Herein, a robust hydrogen-bonded organic framework material (HOF-PTPS) is developed via in-situ incorporation of PEDOT:PSS into a cyano-rich HOF for separator modification. The constructed multiple hydrogen-bonding network and the ordered hierarchical pore structure collaboratively establish rapid Li+ transport channels while effectively inhibiting polysulfides migration. Systematic electrochemical analyses confirm that HOF-PTPS significantly enhances sulfur reaction kinetics, as evidenced by higher Li+ diffusion coefficients, lower polarization, and reduced Tafel slopes. Ex situ and operando characterizations reveal its exceptional capability to anchor polysulfides via strong Li-N coordination, catalyze their conversion, and stabilize key S3·− radicals. Consequently, the HOF-PTPS/PP cell delivers a high reversible capacity of 1172.8 mAh g−1 at 1 C, outstanding cycling stability with 91.4% capacity retention over 500 cycles, and stable operation under high sulfur loading. This work highlights the great potential of multifunctional HOF-based materials in developing high-performance Li-S batteries.
多硫化物的穿梭效应和缓慢的氧化还原动力学严重阻碍了锂硫电池的实际应用。本文通过原位将PEDOT:PSS加入富氰HOF中进行分离器改性，开发了一种坚固的氢键有机框架材料（HOF- ptps）。构建的多重氢键网络和有序的分层孔隙结构共同建立了快速的Li+传输通道，同时有效地抑制了多硫化物的迁移。系统的电化学分析证实，HOF-PTPS显著提高了硫反应动力学，表现为更高的Li+扩散系数、更低的极化和更低的Tafel斜率。非原位和操作位表征揭示了其通过强Li-N配位锚定多硫化物、催化其转化和稳定关键S3·−自由基的卓越能力。因此，HOF-PTPS/PP电池在1℃下具有1172.8 mAh g−1的高可逆容量，在500次循环中具有91.4%的容量保持率，并且在高硫负载下稳定运行。这项工作突出了多功能hof基材料在开发高性能Li-S电池方面的巨大潜力。
{"title":"Multifunctional HOF-Based Heterostructure Enables Advanced Separator Engineering for High-Performance Lithium-Sulfur Batteries","authors":"Zhibin Cheng, Xing Wen, Xiaojing Lin, Weihua Deng, Shengchang Xiang, Banglin Chen, Zhangjing Zhang","doi":"10.31635/ccschem.025.202507126","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507126","url":null,"abstract":"The practical application of lithium-sulfur (Li-S) batteries is severely hampered by the polysulfides shuttle effect and sluggish redox kinetics. Herein, a robust hydrogen-bonded organic framework material (HOF-PTPS) is developed via in-situ incorporation of PEDOT:PSS into a cyano-rich HOF for separator modification. The constructed multiple hydrogen-bonding network and the ordered hierarchical pore structure collaboratively establish rapid Li<sup>+</sup> transport channels while effectively inhibiting polysulfides migration. Systematic electrochemical analyses confirm that HOF-PTPS significantly enhances sulfur reaction kinetics, as evidenced by higher Li<sup>+</sup> diffusion coefficients, lower polarization, and reduced Tafel slopes. Ex situ and operando characterizations reveal its exceptional capability to anchor polysulfides via strong Li-N coordination, catalyze their conversion, and stabilize key S<sub>3</sub>·<sup>−</sup> radicals. Consequently, the HOF-PTPS/PP cell delivers a high reversible capacity of 1172.8 mAh g<sup>−1</sup> at 1 C, outstanding cycling stability with 91.4% capacity retention over 500 cycles, and stable operation under high sulfur loading. This work highlights the great potential of multifunctional HOF-based materials in developing high-performance Li-S batteries.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"31 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072649","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-26DOI: 10.31635/ccschem.025.202507110
Xiaohuan Qin, Xin Wang, Zhengbiao Zhang
Polyurethanes (PUs) are among the most widely used polymers, yet their sustainability is hampered by the reliance on toxic isocyanates in conventional synthesis and inefficient recycling methods. These challenges, together with the growing environmental burden of plastic waste, underscore the urgent need to develop alternative production strategies that utilize renewable feedstocks and enable advanced recycling. In this work, we present a functionalizable and chemically recyclable polyurethane system synthesized via ring-opening polymerization (ROP) of CO2-derived cyclic carbamates. The cyclic monomers were first prepared from CO2 and amino alcohols under mild conditions. Strong base-catalyzed anionic ring-opening polymerization (AROP) allowed controlled polymerization, yielding polyurethanes with good thermal stability and enabling postfunctionalization via thiol-ene “click” chemistry. DFT calculations provided mechanistic evidence for the anionic ring-opening pathway, confirming selective cleavage of the amide C-N bond in the urethane group over the C-O bond. Crucially, efficient depolymerization via vacuum pyrolysis enabled the recovery of the original monomer in high yield, establishing a closed-loop “monomer-polymer-monomer” cycle. This isocyanate-free strategy successfully integrates the utilization of CO2 with advanced chemical recycling and tailorable functionality, offering a versatile and sustainable pathway for advancing the circular economy of polyurethanes.
{"title":"Functionalizable and Chemically Recyclable Polyurethanes via Ring-Opening Polymerization of CO2-Derived Cyclic Carbamates","authors":"Xiaohuan Qin, Xin Wang, Zhengbiao Zhang","doi":"10.31635/ccschem.025.202507110","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507110","url":null,"abstract":"Polyurethanes (PUs) are among the most widely used polymers, yet their sustainability is hampered by the reliance on toxic isocyanates in conventional synthesis and inefficient recycling methods. These challenges, together with the growing environmental burden of plastic waste, underscore the urgent need to develop alternative production strategies that utilize renewable feedstocks and enable advanced recycling. In this work, we present a functionalizable and chemically recyclable polyurethane system synthesized via ring-opening polymerization (ROP) of CO<sub>2</sub>-derived cyclic carbamates. The cyclic monomers were first prepared from CO<sub>2</sub> and amino alcohols under mild conditions. Strong base-catalyzed anionic ring-opening polymerization (AROP) allowed controlled polymerization, yielding polyurethanes with good thermal stability and enabling postfunctionalization via thiol-ene “click” chemistry. DFT calculations provided mechanistic evidence for the anionic ring-opening pathway, confirming selective cleavage of the amide C-N bond in the urethane group over the C-O bond. Crucially, efficient depolymerization via vacuum pyrolysis enabled the recovery of the original monomer in high yield, establishing a closed-loop “monomer-polymer-monomer” cycle. This isocyanate-free strategy successfully integrates the utilization of CO<sub>2</sub> with advanced chemical recycling and tailorable functionality, offering a versatile and sustainable pathway for advancing the circular economy of polyurethanes.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"101 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.31635/ccschem.025.202506897
Haigen Shen, Haiyue Yu, Zhaoxin Shi, Zhaobin Wang
The synthesis of chiral alcohols, which serve as ubiquitous structural motifs in natural products, pharmaceuticals, and bioactive molecules, continues to drive innovation in synthetic methodology. Asymmetric radical carbonyl addition presents a powerful avenue, yet achieving high diastereo- and enantioselectivity with challenging unactivated prochiral alkyl radicals, where subtle differentiation between alkyl substituents is critical, has remained elusive. Herein, we report an unprecedented approach that harnessed noncovalent interactions (NCIs) within a Cr/Ni dual catalytic system to achieve the first highly stereoselective asymmetric carbonyl addition of unactivated prochiral alkyl radicals. This protocol, operating under mild conditions, effectively coupled racemic homobenzylic iodides with diverse range of aryl aldehydes, including axially chiral variants. It provided expedited access to a wide array of synthetically valuable chiral alcohols bearing vicinal stereocenters or multiple stereogenic units (both vicinal stereocenters and axial chirality) with excellent diastereo- and enantiocontrol. Mechanistic insights from density functional theory calculations supported a direct asymmetric radical addition pathway, highlighting the critical role of multiple NCIs in governing the stereochemical outcome.
{"title":"Asymmetric Carbonyl Addition of Unactivated Homobenzyl Radicals Enabled by Noncovalent Interactions","authors":"Haigen Shen, Haiyue Yu, Zhaoxin Shi, Zhaobin Wang","doi":"10.31635/ccschem.025.202506897","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506897","url":null,"abstract":"The synthesis of chiral alcohols, which serve as ubiquitous structural motifs in natural products, pharmaceuticals, and bioactive molecules, continues to drive innovation in synthetic methodology. Asymmetric radical carbonyl addition presents a powerful avenue, yet achieving high diastereo- and enantioselectivity with challenging unactivated prochiral alkyl radicals, where subtle differentiation between alkyl substituents is critical, has remained elusive. Herein, we report an unprecedented approach that harnessed noncovalent interactions (NCIs) within a Cr/Ni dual catalytic system to achieve the first highly stereoselective asymmetric carbonyl addition of unactivated prochiral alkyl radicals. This protocol, operating under mild conditions, effectively coupled racemic homobenzylic iodides with diverse range of aryl aldehydes, including axially chiral variants. It provided expedited access to a wide array of synthetically valuable chiral alcohols bearing vicinal stereocenters or multiple stereogenic units (both vicinal stereocenters and axial chirality) with excellent diastereo- and enantiocontrol. Mechanistic insights from density functional theory calculations supported a direct asymmetric radical addition pathway, highlighting the critical role of multiple NCIs in governing the stereochemical outcome.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"6 1","pages":"1-32"},"PeriodicalIF":11.2,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014769","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-21DOI: 10.31635/ccschem.025.202507117
Zhangyin Yuan, Jing Zhang, Yu-Feng Ren, Hai-Wu Du, Ying Xie, Yulong Li, Qiong Yu, Maoxin Zeng, Wei Shu
Defluorinative cross-coupling under mild conditions in controllable manner is a long-term challenge for the utilization of fluorine-containing compounds. Herein, a photocatalytic triple defluorinative oxygenation enabled [1+2+3] lactonization between trifluoromethyl alkenes and alkenes has been developed, enabling defluorinative alkene-alkene coupling-lactonization to furnish δ-lactones at ambient conditions. A wide range of δ-lactones with different substitution patterns are obtained in one step from two readily available alkenes. By transforming triple C-F bonds to C-O bonds, the reaction features use of water as an oxygen linker for crosscoupling between different alkenes with control of chemo- and regioselectivity as well as a promoter to compensate the enthalpy of C-F bond cleavage.
{"title":"Photocatalytic Triple Defluorinative Oxygenation Enabled [1+2+3] Lactonization: Rapid Synthesis of δ-Lactones from Trifluoromethyl Styrenes","authors":"Zhangyin Yuan, Jing Zhang, Yu-Feng Ren, Hai-Wu Du, Ying Xie, Yulong Li, Qiong Yu, Maoxin Zeng, Wei Shu","doi":"10.31635/ccschem.025.202507117","DOIUrl":"https://doi.org/10.31635/ccschem.025.202507117","url":null,"abstract":"Defluorinative cross-coupling under mild conditions in controllable manner is a long-term challenge for the utilization of fluorine-containing compounds. Herein, a photocatalytic triple defluorinative oxygenation enabled [1+2+3] lactonization between trifluoromethyl alkenes and alkenes has been developed, enabling defluorinative alkene-alkene coupling-lactonization to furnish δ-lactones at ambient conditions. A wide range of δ-lactones with different substitution patterns are obtained in one step from two readily available alkenes. By transforming triple C-F bonds to C-O bonds, the reaction features use of water as an oxygen linker for crosscoupling between different alkenes with control of chemo- and regioselectivity as well as a promoter to compensate the enthalpy of C-F bond cleavage.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"7874 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Fullerene-based materials, particularly [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM), are extensively employed as electron transport materials (ETMs) in inverted perovskite solar cells (PSCs) due to their superior electron transport properties. However, their insufficient passivation capability and tendency to aggregate in films can lead to interfacial charge accumulation and charge carrier recombination losses, ultimately compromising both the efficiency and stability of PSCs. To address these challenges, we developed a novel fullerene derivative, PC61BP, by grafting a cyano-phosphate (CNPhP) functional group to fullerene. The phosphate moiety and –CN group in PC61BP can coordinate with under-coordinated Pb2+ ions on the perovskite surface, facilitating defect passivation and suppressing charge nonradiative recombination. Importantly, the incorporation of the CNPhP group can modulate intermolecular interactions among PC61BP molecules, preventing aggregation and promoting the formation of a more uniform film. Consequently, the inverted devices using PC61BP as the ETM achieve a champion power conversion efficiency (PCE) of 26.01%, markedly outperforming the PC61BM-based control device (PCE = 24.59%), along with improved stability. Moreover, the 1.01 cm2 devices using PC61BP as the ETM achieve a high efficiency of 24.48%. This study offers a promising strategy for advancing the performance of inverted PSCs through the rational design of fullerene-based ETMs.
{"title":"Functional Fullerene Electron Transport Material Beyond PC61BM for Efficient Inverted Perovskite Solar Cells","authors":"Zhenyou Guo, Hang Liu, Yuhan Liu, Yihang Yao, Peiyu Hu, Yuping Gao, Xingbang Gao, Weikai Zhao, Yanna Hou, Wenjuan Feng, Yu Chen, Zhiyuan Xu, Ziyang Hu, Guankui Long, Yongsheng Liu","doi":"10.31635/ccschem.026.202507064","DOIUrl":"https://doi.org/10.31635/ccschem.026.202507064","url":null,"abstract":"Fullerene-based materials, particularly [6,6]-phenyl-C<sub>61</sub>-butyric acid methyl ester (PC<sub>61</sub>BM), are extensively employed as electron transport materials (ETMs) in inverted perovskite solar cells (PSCs) due to their superior electron transport properties. However, their insufficient passivation capability and tendency to aggregate in films can lead to interfacial charge accumulation and charge carrier recombination losses, ultimately compromising both the efficiency and stability of PSCs. To address these challenges, we developed a novel fullerene derivative, PC<sub>61</sub>BP, by grafting a cyano-phosphate (CNPhP) functional group to fullerene. The phosphate moiety and –CN group in PC<sub>61</sub>BP can coordinate with under-coordinated Pb<sup>2+</sup> ions on the perovskite surface, facilitating defect passivation and suppressing charge nonradiative recombination. Importantly, the incorporation of the CNPhP group can modulate intermolecular interactions among PC<sub>61</sub>BP molecules, preventing aggregation and promoting the formation of a more uniform film. Consequently, the inverted devices using PC<sub>61</sub>BP as the ETM achieve a champion power conversion efficiency (PCE) of 26.01%, markedly outperforming the PC<sub>61</sub>BM-based control device (PCE = 24.59%), along with improved stability. Moreover, the 1.01 cm<sup>2</sup> devices using PC<sub>61</sub>BP as the ETM achieve a high efficiency of 24.48%. This study offers a promising strategy for advancing the performance of inverted PSCs through the rational design of fullerene-based ETMs.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"62 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014768","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Epoxide ring opening offers a practical route to alcohols, including enantioenriched variants derived from chiral epoxides. Herein, we report a mild photocatalytic method for generating unconventional, less-substituted alkyl radical intermediates via ring opening of mono-, di-, and tri-substituted epoxides. These radicals undergo hydrogen atom transfer (HAT), primarily with THF (solvent), to deliver branched alcohols as direct reduction products. The reaction proceeds with excellent regioselectivity and tolerates a wide range of reductionsensitive functional groups (e.g., ketone, azide, sulfonyl, cyano, alkene, alkyne, aldehyde, amide, and carbamate). Importantly, this method also enables a unique epoxide remote reduction process. Specifically, when rationally designed and readily accessible enantioenriched epoxides are employed, the direct HAT reduction pathway can be interrupted by radical-mediated intramolecular migration of cyano (CN), (hetero)aryl, or vinyl groups. This process generates remote carbon-, nitrogen-, or oxygen-centered radicals. Subsequent reduction of these intermediates affords enantioenriched β-cyano alcohols, β-amino alcohols, and 1,2-diols, which are useful chiral building blocks. This work introduces an unusual design principle for epoxide ringopening reactions and further expands their synthetic potential.
{"title":"Mild Photocatalysis Enables Both Direct and Remote Reduction of Epoxides","authors":"Jing-Cheng Shi, Meng Zhang, Yi-Fan Yin, Chen Yang, Xianglu Peng, Gang-Wei Wang","doi":"10.31635/ccschem.025.202506968","DOIUrl":"https://doi.org/10.31635/ccschem.025.202506968","url":null,"abstract":"Epoxide ring opening offers a practical route to alcohols, including enantioenriched variants derived from chiral epoxides. Herein, we report a mild photocatalytic method for generating unconventional, less-substituted alkyl radical intermediates via ring opening of mono-, di-, and tri-substituted epoxides. These radicals undergo hydrogen atom transfer (HAT), primarily with THF (solvent), to deliver branched alcohols as direct reduction products. The reaction proceeds with excellent regioselectivity and tolerates a wide range of reductionsensitive functional groups (e.g., ketone, azide, sulfonyl, cyano, alkene, alkyne, aldehyde, amide, and carbamate). Importantly, this method also enables a unique epoxide remote reduction process. Specifically, when rationally designed and readily accessible enantioenriched epoxides are employed, the direct HAT reduction pathway can be interrupted by radical-mediated intramolecular migration of cyano (CN), (hetero)aryl, or vinyl groups. This process generates remote carbon-, nitrogen-, or oxygen-centered radicals. Subsequent reduction of these intermediates affords enantioenriched β-cyano alcohols, β-amino alcohols, and 1,2-diols, which are useful chiral building blocks. This work introduces an unusual design principle for epoxide ringopening reactions and further expands their synthetic potential.","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"32 1","pages":""},"PeriodicalIF":11.2,"publicationDate":"2026-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-18DOI: 10.31635/ccschem.025.202506767
Xiao-Mei Hu, Di-Chang Zhong, Tong-Bu Lu
Acidic electrocatalytic CO2 reduction to high-value multi-carbon (C2+) products is an effective way to achieve high CO2 utilization, where a high concentration of K+ is necessary to suppress hydrogen evolution and promote C-C coupling. However, the high concentration of K+ often leads to salt precipitation, which compromises the stability of the catalytic systems. Herein, we developed a K+ capture strategy to increase the local K+ concentration of Cu nanosheets surface by modifying 4′-aminobenzo-18-crown-6, which can serve as a trap to capture K+ via coordination and confinement. As a result, the modified Cu nanosheets achieved high-performance CO2 electroreduction in acid electrolyte with low concentration of K+. At a current density of −400 mA cm−2, the Faraday efficiency of the C2+ products exceeds 82.3% with a single-pass carbon efficiency (SPCE) of 66.4%, much higher than those of pristine Cu nanosheets. Moreover, the constructed electrocatalytic CO2 reduction system can stably work for over 100 hours. The results of in-situ spectroelectrochemical tests and density functional theory (DFT) calculations reveal that the 4′-aminobenzo-18-crown-6 can really enrich K+ on the Cu nanosheets, which facilitates C-C coupling by promoting CO2 activation and stabilizing *CO intermediates, thereby enabling the preferential conversion of CO2 to C2+ products.
酸性电催化CO2还原成高值多碳（C2+）产物是实现CO2高利用率的有效途径，其中高浓度的K+是抑制析氢和促进C-C耦合的必要条件。然而，高浓度的K+往往会导致盐沉淀，从而影响催化系统的稳定性。在此，我们开发了一种K+捕获策略，通过修饰4 ' -氨基苯-18-冠-6来增加Cu纳米片表面的局部K+浓度，该策略可以通过配位和约束作为捕获K+的陷阱。结果表明，改性后的Cu纳米片在低浓度K+的酸性电解液中实现了高性能的CO2电还原。在−400 mA cm−2的电流密度下，C2+产品的法拉第效率超过82.3%，单次碳效率（SPCE）达到66.4%，大大高于原始Cu纳米片。所构建的电催化CO2还原系统可稳定工作100小时以上。原位光谱电化学测试和密度泛函理论（DFT）计算结果表明，4′-氨基苯-18-冠-6确实可以富集Cu纳米片上的K+，通过促进CO2活化和稳定*CO中间体促进C-C偶联，从而使CO2优先转化为C2+产物。
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