Tandem systems that integrate CO-generating catalysts with copper have shown promise for enhanced carbon dioxide reduction reaction (CO2RR) performance. Sulfur-containing single-atom catalysts are particularly effective for CO production; however, the role and positioning of sulfur in facilitating both CO2-to-CO conversion and tandem CO2RRs remain elusive. Here we show model thiophene-decorated nickel porphyrins as model single-atom catalysts that exhibit tandem activities in the CO2RR. Spectroscopic and theoretical analyses reveal that thiophene substituents induce ligand holes, regulating the d orbitals and d-band centre of the nickel centre to reduce the reaction barrier and promote CO formation. Coupling these single-atom catalysts with a copper catalyst achieves a Faradaic efficiency of 74.3% and a partial current density of 445.8 mA cm−2 for C2 products in a neutral solution, a 46% improvement over bare copper. Operando studies confirm the formation of CO intermediates from the single-atom catalysts, highlighting their role in facilitating tandem catalysis. Model thiophene-decorated nickel porphyrins are synthesized to examine how sulfur promotes CO2-to-CO conversion and tandem CO2-to-C2 product conversion in electrocatalytic CO2 reduction. Combined theoretical and experimental analyses show that thiophene substituents generate a ligand hole character that modulates the nickel-centred electronic structure, enhancing overall catalytic performance.
将co生成催化剂与铜相结合的串联系统有望提高二氧化碳还原反应（CO2RR）的性能。含硫单原子催化剂对CO生产特别有效；然而，硫在促进CO2-to-CO转化和串联co2rs中的作用和定位仍然难以捉摸。在这里，我们展示了模型噻吩修饰的镍卟啉作为模型单原子催化剂，在CO2RR中表现出串联活性。光谱和理论分析表明，噻吩取代基诱导配体空穴，调节镍中心的d轨道和d带中心，降低反应势垒，促进CO的生成。将这些单原子催化剂与铜催化剂耦合，在中性溶液中，C2产品的法拉第效率为74.3%，分电流密度为445.8 mA cm - 2，比裸铜提高46%。Operando研究证实了单原子催化剂中CO中间体的形成，突出了它们在促进串联催化中的作用。合成了噻吩修饰的镍卟啉模型，以研究硫在电催化CO2还原中如何促进CO2- co转化和串联CO2- c2产物转化。结合理论和实验分析表明，噻吩取代基产生一个配体空穴特征，调节镍中心电子结构，提高整体催化性能。
{"title":"Model thiophene-decorated nickel porphyrins for tandem CO2 reduction","authors":"Yi-Hsuan Lu, Yu-Jhih Shen, Hsin-Jung Tsai, Yen-Hua Lee, Yong-Yi Huang, Zih-Yi Lin, Wen-Yang Huang, Tsung-Ju Lee, Guan-Lin Chen, Nozomu Hiraoka, Hirofumi Ishii, Hsueh-Ju Liu, Shao-Hui Hsu, Chun-Chih Chang, Aoni Xu, Sung-Fu Hung","doi":"10.1038/s44160-025-00903-7","DOIUrl":"10.1038/s44160-025-00903-7","url":null,"abstract":"Tandem systems that integrate CO-generating catalysts with copper have shown promise for enhanced carbon dioxide reduction reaction (CO2RR) performance. Sulfur-containing single-atom catalysts are particularly effective for CO production; however, the role and positioning of sulfur in facilitating both CO2-to-CO conversion and tandem CO2RRs remain elusive. Here we show model thiophene-decorated nickel porphyrins as model single-atom catalysts that exhibit tandem activities in the CO2RR. Spectroscopic and theoretical analyses reveal that thiophene substituents induce ligand holes, regulating the d orbitals and d-band centre of the nickel centre to reduce the reaction barrier and promote CO formation. Coupling these single-atom catalysts with a copper catalyst achieves a Faradaic efficiency of 74.3% and a partial current density of 445.8 mA cm−2 for C2 products in a neutral solution, a 46% improvement over bare copper. Operando studies confirm the formation of CO intermediates from the single-atom catalysts, highlighting their role in facilitating tandem catalysis. Model thiophene-decorated nickel porphyrins are synthesized to examine how sulfur promotes CO2-to-CO conversion and tandem CO2-to-C2 product conversion in electrocatalytic CO2 reduction. Combined theoretical and experimental analyses show that thiophene substituents generate a ligand hole character that modulates the nickel-centred electronic structure, enhancing overall catalytic performance.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"189-198"},"PeriodicalIF":20.0,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146155308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-08DOI: 10.1038/s44160-025-00906-4
Eric J. Piechota
{"title":"Palladium makes agostic C–H bonds more acidic","authors":"Eric J. Piechota","doi":"10.1038/s44160-025-00906-4","DOIUrl":"10.1038/s44160-025-00906-4","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 10","pages":"1174-1174"},"PeriodicalIF":20.0,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256850","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-01DOI: 10.1038/s44160-025-00910-8
Charge-selective contacts have a key role in increasing the efficiency of perovskite solar cells (PSCs). A hole-transport material (HTM) is designed based on a symmetric aromatic molecule that facilitates long-range ordered π–π stacking on substrates. This HTM shows enhanced charge-transport properties, and when incorporated into PSCs, helps to deliver good efficiency and stability.
{"title":"Symmetric molecules for long-range ordered π–π stacked hole-transport materials","authors":"","doi":"10.1038/s44160-025-00910-8","DOIUrl":"10.1038/s44160-025-00910-8","url":null,"abstract":"Charge-selective contacts have a key role in increasing the efficiency of perovskite solar cells (PSCs). A hole-transport material (HTM) is designed based on a symmetric aromatic molecule that facilitates long-range ordered π–π stacking on substrates. This HTM shows enhanced charge-transport properties, and when incorporated into PSCs, helps to deliver good efficiency and stability.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":"12-13"},"PeriodicalIF":20.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145958197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The development of molecular engineering has substantially increased the power conversion efficiency of inverted p-i-n perovskite solar cells (PSCs) over the past five years, surpassing that of regular n-i-p PSCs. The strategic design of symmetric molecules to alleviate steric hindrance, thereby facilitating long-range-ordered π–π stacking on substrates, offers an effective approach for enhancing the structural organization in molecular self-assembly. Here we synthesize an axially symmetric molecule with homogeneous electron delocalization, (2-(pyren-2-yl)ethyl)phosphonic acid (pPy), which can form a long-range-ordered π–π stacking assembly on indium tin oxide substrates. Additionally, the pPy thin film demonstrates an intense and integrated Debye–Scherrer ring at q = 0.27 Å−1 with a highly ordered face-on orientation and displays more spatial uniform distribution, which effectively facilitates charge transport. The as-fabricated pPy-based PSCs achieve a power conversion efficiency of 26.6% and maintain 94% of the initial efficiency after 3,000 h of continuous simulated solar illumination following the ISOS-L-1I protocol. Molecular engineering has increased the power conversion efficiency of inverted perovskite solar cells (PSCs), surpassing that of regular PSCs. Here, the symmetric molecule (2-(pyren-2-yl)ethyl)phosphonic acid (pPy) enables long-range-ordered π–π stacking, enhancing charge transport. pPy films show face-on orientation and uniform distribution, yielding PSCs with power conversion efficiencies of 26.6%.
{"title":"Symmetry-driven engineering of long-range-ordered π–π stacking molecules for high-efficiency perovskite photovoltaics","authors":"Peide Zhu, Zhixin Liu, Xia Lei, Siru He, Deng Wang, Jie Zeng, Lida Wang, Fei Su, Wenbo Peng, Zheng Liang, Yuxin Sun, Zhiwei Lei, Zhitong Li, Hsien-Yi Hsu, Xu Pan, Xingzhu Wang, Jingbai Li, Yong Zhang, Baomin Xu","doi":"10.1038/s44160-025-00896-3","DOIUrl":"10.1038/s44160-025-00896-3","url":null,"abstract":"The development of molecular engineering has substantially increased the power conversion efficiency of inverted p-i-n perovskite solar cells (PSCs) over the past five years, surpassing that of regular n-i-p PSCs. The strategic design of symmetric molecules to alleviate steric hindrance, thereby facilitating long-range-ordered π–π stacking on substrates, offers an effective approach for enhancing the structural organization in molecular self-assembly. Here we synthesize an axially symmetric molecule with homogeneous electron delocalization, (2-(pyren-2-yl)ethyl)phosphonic acid (pPy), which can form a long-range-ordered π–π stacking assembly on indium tin oxide substrates. Additionally, the pPy thin film demonstrates an intense and integrated Debye–Scherrer ring at q = 0.27 Å−1 with a highly ordered face-on orientation and displays more spatial uniform distribution, which effectively facilitates charge transport. The as-fabricated pPy-based PSCs achieve a power conversion efficiency of 26.6% and maintain 94% of the initial efficiency after 3,000 h of continuous simulated solar illumination following the ISOS-L-1I protocol. Molecular engineering has increased the power conversion efficiency of inverted perovskite solar cells (PSCs), surpassing that of regular PSCs. Here, the symmetric molecule (2-(pyren-2-yl)ethyl)phosphonic acid (pPy) enables long-range-ordered π–π stacking, enhancing charge transport. pPy films show face-on orientation and uniform distribution, yielding PSCs with power conversion efficiencies of 26.6%.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":"64-73"},"PeriodicalIF":20.0,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145958198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The enantioselective transformation of alcohols into three-dimensional chiral molecules via C–C bond cleavage remains a substantial challenge in synthetic chemistry. In this study, an amino alcohol was used as a coupling partner to achieve asymmetric C(sp3)–C(sp2) cross-coupling by integrating electrochemistry, ligand-to-metal charge transfer photocatalysis and asymmetric nickel catalysis. Notably, this work represents the application of alternating current in paired photo-electrocatalysis, substantially enhancing the reactivity of photo-electrochemical reactions. This approach disrupts the electrostatic interactions that anchor transition metal complexes within the electric double layer, preventing their accumulation on electrode surfaces and thereby improving catalytic efficiency, stability and long-term system performance. The platform accommodates a broad range of substrates, achieving exceptional enantioselectivities up to 99% enantiomeric excess and enabling late-stage diversification of complex, medicinally relevant molecules. Both experimental investigations and density functional theory calculations provide insights into the reaction mechanism and the origin of enantioselectivity in the asymmetric cross-coupling of alcohols. An alternating current paired photo-electrocatalysis approach, integrating electrochemistry, ligand-to-metal charge transfer photocatalysis and asymmetric nickel catalysis, enables enantioselective C(sp3)–C(sp2) cross-coupling of alcohols. This approach has high catalytic efficiency and stability, achieving up to 99% enantiomeric excess with broad substrate compatibility, and is suitable for late-stage functionalization of complex molecules.
{"title":"Applying alternating current in paired photo-electrocatalysis for asymmetric cross-coupling of alcohols","authors":"Wei Liu, Cai Zhai, Yong Jiang, Li-Pu Wei, Hong-Chen Li, Zongwei Cai, Chen Zhu","doi":"10.1038/s44160-025-00875-8","DOIUrl":"10.1038/s44160-025-00875-8","url":null,"abstract":"The enantioselective transformation of alcohols into three-dimensional chiral molecules via C–C bond cleavage remains a substantial challenge in synthetic chemistry. In this study, an amino alcohol was used as a coupling partner to achieve asymmetric C(sp3)–C(sp2) cross-coupling by integrating electrochemistry, ligand-to-metal charge transfer photocatalysis and asymmetric nickel catalysis. Notably, this work represents the application of alternating current in paired photo-electrocatalysis, substantially enhancing the reactivity of photo-electrochemical reactions. This approach disrupts the electrostatic interactions that anchor transition metal complexes within the electric double layer, preventing their accumulation on electrode surfaces and thereby improving catalytic efficiency, stability and long-term system performance. The platform accommodates a broad range of substrates, achieving exceptional enantioselectivities up to 99% enantiomeric excess and enabling late-stage diversification of complex, medicinally relevant molecules. Both experimental investigations and density functional theory calculations provide insights into the reaction mechanism and the origin of enantioselectivity in the asymmetric cross-coupling of alcohols. An alternating current paired photo-electrocatalysis approach, integrating electrochemistry, ligand-to-metal charge transfer photocatalysis and asymmetric nickel catalysis, enables enantioselective C(sp3)–C(sp2) cross-coupling of alcohols. This approach has high catalytic efficiency and stability, achieving up to 99% enantiomeric excess with broad substrate compatibility, and is suitable for late-stage functionalization of complex molecules.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 12","pages":"1534-1545"},"PeriodicalIF":20.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145706668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-29DOI: 10.1038/s44160-025-00878-5
Zibo Bai, Tobias Ritter
Thianthrene was first reported in 1869 and has been widely used in materials science for redox-flow batteries, polymers, supramolecular chemistry and phosphorescent materials. Despite extensive studies of the thianthrene radical cation and its reactivity since 1957, applications of thianthrene in synthetic chemistry were virtually absent from the literature until 2019. The then-discovered unusually high selectivity for thianthrenation by electrophilic aromatic substitution allowed for the synthesis of single constitutional isomers of structurally complex aryl-thianthrenium salts, which were mostly used as aryl (pseudo)halide analogues for subsequent functionalization. Since then, it has become apparent that the electronic structure of the thianthrenium substituent enables reaction chemistry that in part goes beyond what can be achieved with conventional organo(pseudo)halides. In this Review, we analyse and explain the fundamental aspects of organothianthrene chemistry, highlight the difference in reactivity to conventional organo(pseudo)halides and showcase its diverse applications. Thianthrene, long used in materials science, has recently emerged as a powerful reagent in organic synthesis. Its unique electronic structure enables access to diverse aryl, alkenyl and alkyl thianthrenium salts, which exhibit reactivity beyond conventional (pseudo)halides. This Review highlights the fundamental properties, distinctive reactivity and synthetic applications of these thianthrenium salts.
{"title":"Applications of thianthrene chemistry in organic synthesis","authors":"Zibo Bai, Tobias Ritter","doi":"10.1038/s44160-025-00878-5","DOIUrl":"10.1038/s44160-025-00878-5","url":null,"abstract":"Thianthrene was first reported in 1869 and has been widely used in materials science for redox-flow batteries, polymers, supramolecular chemistry and phosphorescent materials. Despite extensive studies of the thianthrene radical cation and its reactivity since 1957, applications of thianthrene in synthetic chemistry were virtually absent from the literature until 2019. The then-discovered unusually high selectivity for thianthrenation by electrophilic aromatic substitution allowed for the synthesis of single constitutional isomers of structurally complex aryl-thianthrenium salts, which were mostly used as aryl (pseudo)halide analogues for subsequent functionalization. Since then, it has become apparent that the electronic structure of the thianthrenium substituent enables reaction chemistry that in part goes beyond what can be achieved with conventional organo(pseudo)halides. In this Review, we analyse and explain the fundamental aspects of organothianthrene chemistry, highlight the difference in reactivity to conventional organo(pseudo)halides and showcase its diverse applications. Thianthrene, long used in materials science, has recently emerged as a powerful reagent in organic synthesis. Its unique electronic structure enables access to diverse aryl, alkenyl and alkyl thianthrenium salts, which exhibit reactivity beyond conventional (pseudo)halides. This Review highlights the fundamental properties, distinctive reactivity and synthetic applications of these thianthrenium salts.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 10","pages":"1187-1199"},"PeriodicalIF":20.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-29DOI: 10.1038/s44160-025-00897-2
Samrat Mallick, Suman De Sarkar
Photo-electrocatalysis under alternating polarity allows enantioselective redox-neutral cross-coupling through β-scission of alcohols to afford optically pure chiral α-arylated amines.
{"title":"Alternating polarity photo-electrocatalysis for asymmetric C−C cross-couplings","authors":"Samrat Mallick, Suman De Sarkar","doi":"10.1038/s44160-025-00897-2","DOIUrl":"10.1038/s44160-025-00897-2","url":null,"abstract":"Photo-electrocatalysis under alternating polarity allows enantioselective redox-neutral cross-coupling through β-scission of alcohols to afford optically pure chiral α-arylated amines.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 12","pages":"1481-1482"},"PeriodicalIF":20.0,"publicationDate":"2025-09-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145706663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Although covalent organic framework (COF)-based photocatalysts show advantages in visible-light-driven photocatalytic hydrogen peroxide (H2O2) production, enhancing the photogenerated carrier transfer efficiency to boost overall H2O2 production remains challenging. Here, based on Schiff base reactions of 2,4,6-triformylphloroglucinol (Tp) with p-phenylenediamine (Pa) and 3,6-pyridazinediamine (Dz), a COF/COF type-II heterojunction, TpPa/TpDz, was constructed. TpPa/TpDz achieved a photocatalytic H2O2 production of 24.42 mmol g−1 h−1 in pure water, demonstrating exceptional performance among organic material-based photocatalysts under comparable conditions. Mechanism studies revealed that the almost complete separation of the highest occupied and lowest unoccupied molecular orbitals in the type-II heterojunction allows efficient and directional transport of photogenerated carriers, enabling efficient photocatalytic H2O2 synthesis. This work illustrates the advantages of the design of COF-based heterojunction photocatalysts for H2O2 production, offering insights and strategies for developing high-performance COF-based systems for the synthesis of value-added products. A covalent organic framework-based type-II heterojunction (TpPa/TpDz) enables efficient photocatalytic H2O2 production in pure water. The highest and lowest occupied molecular orbitals are spatially separated, driving directional photogenerated carrier transport and minimizing recombination, therefore enhancing photocatalytic activity.
{"title":"Engineering a covalent organic framework-based type-II heterojunction for enhanced photocatalytic H2O2 synthesis","authors":"Hongyan Guo, Shiyong Wang, Xin Chen, Jingfang Kou, Guoqiang He, Zhengping Dong, Yong Yan","doi":"10.1038/s44160-025-00880-x","DOIUrl":"10.1038/s44160-025-00880-x","url":null,"abstract":"Although covalent organic framework (COF)-based photocatalysts show advantages in visible-light-driven photocatalytic hydrogen peroxide (H2O2) production, enhancing the photogenerated carrier transfer efficiency to boost overall H2O2 production remains challenging. Here, based on Schiff base reactions of 2,4,6-triformylphloroglucinol (Tp) with p-phenylenediamine (Pa) and 3,6-pyridazinediamine (Dz), a COF/COF type-II heterojunction, TpPa/TpDz, was constructed. TpPa/TpDz achieved a photocatalytic H2O2 production of 24.42 mmol g−1 h−1 in pure water, demonstrating exceptional performance among organic material-based photocatalysts under comparable conditions. Mechanism studies revealed that the almost complete separation of the highest occupied and lowest unoccupied molecular orbitals in the type-II heterojunction allows efficient and directional transport of photogenerated carriers, enabling efficient photocatalytic H2O2 synthesis. This work illustrates the advantages of the design of COF-based heterojunction photocatalysts for H2O2 production, offering insights and strategies for developing high-performance COF-based systems for the synthesis of value-added products. A covalent organic framework-based type-II heterojunction (TpPa/TpDz) enables efficient photocatalytic H2O2 production in pure water. The highest and lowest occupied molecular orbitals are spatially separated, driving directional photogenerated carrier transport and minimizing recombination, therefore enhancing photocatalytic activity.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 12","pages":"1610-1620"},"PeriodicalIF":20.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145706671","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-09-24DOI: 10.1038/s44160-025-00895-4
Zhuoer Li, Shanshan Tao, Matthew Addicoat, Toshikazu Nakamura, Donglin Jiang
Covalent organic frameworks (COFs) are crystalline porous polymers traditionally assembled via reversible condensation polymerizations to form ordered structures. In contrast, coupling reactions have historically led to amorphous, disordered materials due to their irreversible nature, posing a challenge for COF synthesis. Here we present a microinterfacial solvothermal polymerization strategy that overcomes this limitation by harnessing irreversible coupling reactions to construct crystalline porous framework materials. By spatially confining monomers and intermediates at organic–water interfaces, our approach drives Glaser–Eglinton coupling polymerization of ethynyl-functionalized monomers to form two-dimensional sp-carbon-conjugated COFs with discrete hexagonal, tetragonal and kagome topologies. The resulting frameworks allow extended in-plane π conjugation and out-of-plane electronic coupling and exhibit an eight-order-of-magnitude enhancement in electrical conductivity upon chemical oxidation with iodine in pores. These materials confine free radicals at nodal sites, where their spins are aligned in different ways to develop paramagnetic, antiferromagnetic and ferromagnetic phases, evolving semiconducting magnets with distinct spin coherence controlled by the COF topology. These findings showcase the use of coupling reactions in COF synthesis to synthesize an interesting class of organic semiconducting magnets. A microinterfacial solvothermal polymerization strategy is developed for irreversible coupling reactions to form porous crystalline sp-carbon-conjugated covalent organic frameworks with diverse topologies. These two-dimensional frameworks exhibit enhanced conductivity and tunable magnetic properties.
{"title":"Synthesis of covalent organic frameworks via coupling polymerization","authors":"Zhuoer Li, Shanshan Tao, Matthew Addicoat, Toshikazu Nakamura, Donglin Jiang","doi":"10.1038/s44160-025-00895-4","DOIUrl":"10.1038/s44160-025-00895-4","url":null,"abstract":"Covalent organic frameworks (COFs) are crystalline porous polymers traditionally assembled via reversible condensation polymerizations to form ordered structures. In contrast, coupling reactions have historically led to amorphous, disordered materials due to their irreversible nature, posing a challenge for COF synthesis. Here we present a microinterfacial solvothermal polymerization strategy that overcomes this limitation by harnessing irreversible coupling reactions to construct crystalline porous framework materials. By spatially confining monomers and intermediates at organic–water interfaces, our approach drives Glaser–Eglinton coupling polymerization of ethynyl-functionalized monomers to form two-dimensional sp-carbon-conjugated COFs with discrete hexagonal, tetragonal and kagome topologies. The resulting frameworks allow extended in-plane π conjugation and out-of-plane electronic coupling and exhibit an eight-order-of-magnitude enhancement in electrical conductivity upon chemical oxidation with iodine in pores. These materials confine free radicals at nodal sites, where their spins are aligned in different ways to develop paramagnetic, antiferromagnetic and ferromagnetic phases, evolving semiconducting magnets with distinct spin coherence controlled by the COF topology. These findings showcase the use of coupling reactions in COF synthesis to synthesize an interesting class of organic semiconducting magnets. A microinterfacial solvothermal polymerization strategy is developed for irreversible coupling reactions to form porous crystalline sp-carbon-conjugated covalent organic frameworks with diverse topologies. These two-dimensional frameworks exhibit enhanced conductivity and tunable magnetic properties.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"199-208"},"PeriodicalIF":20.0,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146155312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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