Layered organic–inorganic hybrid superlattices, with modular structural advantages, offer an interesting approach to overcome the challenges in modulating the efficiency of intersystem crossing (ISC). This hybrid material system integrates the variable electronic and atomic properties of inorganic metal layers with the programmable chemical properties of organic coordination layers, enabling regulation of electronic states, excitons and ISC processes. Here we demonstrate a precise ISC modulating strategy by constructing gold-based organic–inorganic layered hybrid superlattices, featuring alternately assembled atomically thin gold layers and 4-mercapto-benzamide-derived organic ligands layers. The confined layered structure achieves directional hybridization between transition metal d orbitals and delocalized electrons of organic moieties through controlled Au–π conjugation interactions. Femtosecond transient-absorption spectroscopy reveals that ISC time decreases from >2 ps to 0.26 ps as interlayer spacing reduces, demonstrating the role of structural confinement in promoting ultrafast ISC. Moreover, temperature-dependent photoluminescence studies estimate the singlet–triplet energy gap at ∼20 meV, further supporting the enhanced ISC mechanism. This work introduces the design of hybrid superlattices with tailored spin–orbit interactions enabling tunable fluorescence and phosphorescence properties, paving the way for next-generation optoelectronic applications. Gold-based layered hybrid superlattices with tunable interlayer spacing are synthesized as an efficient strategy to modulate intersystem crossing (ISC). Reduced interlayer spacing enhances Au–π conjugation, accelerating the ISC to 0.26 ps and enabling tailored spin–orbit interactions for advanced optoelectronic applications.
{"title":"Layered hybrid superlattices with a regulated intersystem crossing process","authors":"Haosen Yang, Yutong Zhang, Zhengyao Qiu, Hongfei Gu, He Guo, Tianqi Guo, Pengfei Hu, Lingyun Zhu, Shuai Yue, Xinfeng Liu, Lin Guo","doi":"10.1038/s44160-025-00921-5","DOIUrl":"10.1038/s44160-025-00921-5","url":null,"abstract":"Layered organic–inorganic hybrid superlattices, with modular structural advantages, offer an interesting approach to overcome the challenges in modulating the efficiency of intersystem crossing (ISC). This hybrid material system integrates the variable electronic and atomic properties of inorganic metal layers with the programmable chemical properties of organic coordination layers, enabling regulation of electronic states, excitons and ISC processes. Here we demonstrate a precise ISC modulating strategy by constructing gold-based organic–inorganic layered hybrid superlattices, featuring alternately assembled atomically thin gold layers and 4-mercapto-benzamide-derived organic ligands layers. The confined layered structure achieves directional hybridization between transition metal d orbitals and delocalized electrons of organic moieties through controlled Au–π conjugation interactions. Femtosecond transient-absorption spectroscopy reveals that ISC time decreases from >2 ps to 0.26 ps as interlayer spacing reduces, demonstrating the role of structural confinement in promoting ultrafast ISC. Moreover, temperature-dependent photoluminescence studies estimate the singlet–triplet energy gap at ∼20 meV, further supporting the enhanced ISC mechanism. This work introduces the design of hybrid superlattices with tailored spin–orbit interactions enabling tunable fluorescence and phosphorescence properties, paving the way for next-generation optoelectronic applications. Gold-based layered hybrid superlattices with tunable interlayer spacing are synthesized as an efficient strategy to modulate intersystem crossing (ISC). Reduced interlayer spacing enhances Au–π conjugation, accelerating the ISC to 0.26 ps and enabling tailored spin–orbit interactions for advanced optoelectronic applications.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"272-280"},"PeriodicalIF":20.0,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145498913","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 : 2025-11-11DOI: 10.1038/s44160-025-00931-3
Kaiqi Li, Xiaoyue Sun, Qikai Wu, Chuanbiao Zhang, Dan Wang, Shuai Guo, Xiaofei Chen, Xiaoting Chen, Tianding Xu, Ran Du, Yao Yang, Zhiyuan He
High-entropy alloys (HEAs) are usually synthesized by stabilizing thermodynamically metastable structures from high temperatures. Here we present a bilayer ice recrystallization approach performed at subzero temperatures to synthesize HEA nanoparticles or aerogels with up to 11 metal elements. We found that, below 0 °C, premelted ice channels can regulate the uniform emission of metal salts and reductants to form HEA seeds. The seeds function as anti-icing agents akin to antifreeze proteins, promoting uniform element mixing and assembly at ice grain boundaries to form HEA nanoparticles or HEA aerogels. In addition, by introducing an arbitrary template, we synthesized nanometre-thick uniform HEA coatings on diverse metal or alloy nanoparticles and macroscale aerogels. The bilayer ice recrystallization method demonstrates the application of ice chemistry for the synthesis of high-entropy-based materials with hierarchical architectures. High-entropy alloy (HEA) nanoparticles, self-supporting HEA aerogels and HEA coatings with up to 11 metal elements and uniform elemental distributions have been synthesized at subzero temperatures using a bilayer ice recrystallization method. The process is observed by cryo-transmission electron microscopy and fused multimodal electron tomography.
{"title":"Synthesizing high-entropy alloy materials and coatings using a bilayer ice recrystallization method","authors":"Kaiqi Li, Xiaoyue Sun, Qikai Wu, Chuanbiao Zhang, Dan Wang, Shuai Guo, Xiaofei Chen, Xiaoting Chen, Tianding Xu, Ran Du, Yao Yang, Zhiyuan He","doi":"10.1038/s44160-025-00931-3","DOIUrl":"10.1038/s44160-025-00931-3","url":null,"abstract":"High-entropy alloys (HEAs) are usually synthesized by stabilizing thermodynamically metastable structures from high temperatures. Here we present a bilayer ice recrystallization approach performed at subzero temperatures to synthesize HEA nanoparticles or aerogels with up to 11 metal elements. We found that, below 0 °C, premelted ice channels can regulate the uniform emission of metal salts and reductants to form HEA seeds. The seeds function as anti-icing agents akin to antifreeze proteins, promoting uniform element mixing and assembly at ice grain boundaries to form HEA nanoparticles or HEA aerogels. In addition, by introducing an arbitrary template, we synthesized nanometre-thick uniform HEA coatings on diverse metal or alloy nanoparticles and macroscale aerogels. The bilayer ice recrystallization method demonstrates the application of ice chemistry for the synthesis of high-entropy-based materials with hierarchical architectures. High-entropy alloy (HEA) nanoparticles, self-supporting HEA aerogels and HEA coatings with up to 11 metal elements and uniform elemental distributions have been synthesized at subzero temperatures using a bilayer ice recrystallization method. The process is observed by cryo-transmission electron microscopy and fused multimodal electron tomography.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"302-312"},"PeriodicalIF":20.0,"publicationDate":"2025-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145485152","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 : 2025-11-10DOI: 10.1038/s44160-025-00937-x
Cade A. MacAllister, Caitlin R. Lacker, Matthieu F. Maciejewski, Felix Wessels, Desiree M. Bates, Scott W. Bagley, Tehshik P. Yoon
{"title":"Oxygen migration into carbon–carbon single bonds by photochemical oxidation","authors":"Cade A. MacAllister, Caitlin R. Lacker, Matthieu F. Maciejewski, Felix Wessels, Desiree M. Bates, Scott W. Bagley, Tehshik P. Yoon","doi":"10.1038/s44160-025-00937-x","DOIUrl":"https://doi.org/10.1038/s44160-025-00937-x","url":null,"abstract":"","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"98 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145478209","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 need for sustainable alternatives to petroleum-based polymers has driven the development of advanced catalysts for polyester synthesis. Here we present a series of covalently tethered borane–oxyanion organocatalysts for the ring-opening copolymerization of epoxides and cyclic anhydrides. These catalysts achieve outstanding efficiency, with turnover frequencies up to 13,500 h−1 and high molecular weights (Mn) up to 174.0 kDa of the resultant polymers. Mechanistic studies reveal that intramolecular cooperation between borane and propagating species accelerates the rate-limiting epoxide ring-opening step, resulting in nearly equivalent energy barriers for epoxide and anhydride ring opening. Notably, the covalent tethering strategy not only enhances performance but also imparts remarkable air stability, addressing key limitations of conventional borane-based catalysts. Furthermore, our catalysts exhibit broad substrate scope and high thermal stability, facilitating the production of metal-free polyesters with tailored characteristics. This work establishes a sustainable and robust platform for polyester synthesis, with promising applications in biomaterials and packaging. Covalently tethered borane–oxyanion organocatalysts enable highly efficient ring-opening copolymerization of epoxides and cyclic anhydrides via intramolecular cooperation, achieving turnover frequencies up to 13,500 h−1 and high molecular weights up to 174.0 kDa. These catalysts feature air stability, broad substrate scope, thermal stability and metal-free polyester production.
{"title":"Air-stable covalent borane–oxyanion organocatalysts for ring-opening copolymerization","authors":"Ximin Feng, Xiong Liu, Xun Zhang, Wenqi Guo, Chengjian Zhang, Xinghong Zhang","doi":"10.1038/s44160-025-00923-3","DOIUrl":"10.1038/s44160-025-00923-3","url":null,"abstract":"The need for sustainable alternatives to petroleum-based polymers has driven the development of advanced catalysts for polyester synthesis. Here we present a series of covalently tethered borane–oxyanion organocatalysts for the ring-opening copolymerization of epoxides and cyclic anhydrides. These catalysts achieve outstanding efficiency, with turnover frequencies up to 13,500 h−1 and high molecular weights (Mn) up to 174.0 kDa of the resultant polymers. Mechanistic studies reveal that intramolecular cooperation between borane and propagating species accelerates the rate-limiting epoxide ring-opening step, resulting in nearly equivalent energy barriers for epoxide and anhydride ring opening. Notably, the covalent tethering strategy not only enhances performance but also imparts remarkable air stability, addressing key limitations of conventional borane-based catalysts. Furthermore, our catalysts exhibit broad substrate scope and high thermal stability, facilitating the production of metal-free polyesters with tailored characteristics. This work establishes a sustainable and robust platform for polyester synthesis, with promising applications in biomaterials and packaging. Covalently tethered borane–oxyanion organocatalysts enable highly efficient ring-opening copolymerization of epoxides and cyclic anhydrides via intramolecular cooperation, achieving turnover frequencies up to 13,500 h−1 and high molecular weights up to 174.0 kDa. These catalysts feature air stability, broad substrate scope, thermal stability and metal-free polyester production.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"251-261"},"PeriodicalIF":20.0,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145447775","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 : 2025-11-06DOI: 10.1038/s44160-025-00919-z
Ethan R. X. Lim, Bradley D. Cooper, Muralidharan Shanmugam, Jonathan Da Luz, Eric J. L. McInnes, Cristina Trujillo, James J. Douglas, Michael J. James
Radical chain initiation strategies are fundamental to the synthesis of small molecule drugs and macromolecular materials. Modern methods for initiation through one-electron reduction are largely dominated by photo- and electrochemistry but the large-scale industrial application of these methods is often hampered by scalability challenges. Here we report a general, thermally driven and scalable method for the reductive initiation of radical chains that involves reacting an inexpensive azo initiator with a formate salt to form a carbon dioxide radical anion. Substoichiometric quantities of this initiator system were used to form C(sp2)–C(sp3), C(sp2)–S, C(sp2)–H, C(sp2)–B and C(sp2)–P bonds from complex (hetero)aryl halides, with high chemoselectivity and under transition-metal-free conditions. The developed initiator system was also used to probe the mechanism of other radical reactions. Radical chain initiation strategies are fundamental to the synthesis of small molecule drugs and macromolecular materials. Here a general, thermally driven and scalable method for reductive initiation is reported, in which inexpensive azo initiators are reacted with formate salts to form a carbon dioxide radical anion.
{"title":"Reductive radical chain initiation through the thermal generation of carbon dioxide radical anion","authors":"Ethan R. X. Lim, Bradley D. Cooper, Muralidharan Shanmugam, Jonathan Da Luz, Eric J. L. McInnes, Cristina Trujillo, James J. Douglas, Michael J. James","doi":"10.1038/s44160-025-00919-z","DOIUrl":"10.1038/s44160-025-00919-z","url":null,"abstract":"Radical chain initiation strategies are fundamental to the synthesis of small molecule drugs and macromolecular materials. Modern methods for initiation through one-electron reduction are largely dominated by photo- and electrochemistry but the large-scale industrial application of these methods is often hampered by scalability challenges. Here we report a general, thermally driven and scalable method for the reductive initiation of radical chains that involves reacting an inexpensive azo initiator with a formate salt to form a carbon dioxide radical anion. Substoichiometric quantities of this initiator system were used to form C(sp2)–C(sp3), C(sp2)–S, C(sp2)–H, C(sp2)–B and C(sp2)–P bonds from complex (hetero)aryl halides, with high chemoselectivity and under transition-metal-free conditions. The developed initiator system was also used to probe the mechanism of other radical reactions. Radical chain initiation strategies are fundamental to the synthesis of small molecule drugs and macromolecular materials. Here a general, thermally driven and scalable method for reductive initiation is reported, in which inexpensive azo initiators are reacted with formate salts to form a carbon dioxide radical anion.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"221-229"},"PeriodicalIF":20.0,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00919-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145448097","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-06DOI: 10.1038/s44160-025-00920-6
Yu-Xiu Li, Cheng-Hao Zong, Yu Meng, Lei Jiao
Direct access to multifunctionalized arenes through regioselective vicinal difunctionalization of aryl substrates is a challenging yet highly sought-after process. Palladium–norbornene catalysis enables the synthesis of ipso,ortho-difunctionalized products from haloarenes; however, selective mono-ortho-alkylative vicinal difunctionalization reactions of para-substituted haloarene substrates have remained elusive. Here we report the use of a methyl-modified thio-cycloolefin ligand for the palladium-catalysed ortho-alkylative vicinal difunctionalization of para-substituted iodoarenes. This catalytic system demonstrates compatibility with a variety of para-substituted iodoarenes, alkyl iodides and termination reagents, facilitating ortho-alkylative vicinal difunctionalization unattainable by conventional palladium–norbornene catalysis. In addition, the catalytic system can be used for the selective mono-ortho-arylation of para-substituted iodoarenes, enabling the synthesis of triphenylenes. Mechanistic studies reveal the origins of site selectivity within the catalytic process, through isolation of key intermediates and examination of their stoichiometric reactivity. This work highlights the versatility of palladium–olefin catalysis in addressing the complexities associated with constructing multifunctionalized aromatic frameworks through rational molecular design. Palladium–olefin catalysis is utilized to overcome the ‘ortho constraint’ in the Catellani reaction of para-substituted iodoarenes. Using a methyl-modified thio-cycloolefin ligand, this method enables selective mono-alkylative vicinal difunctionalization of para-substituted iodoarenes, which is unattainable by conventional palladium–norbornene catalysis.
{"title":"Complementary site selectivity in ortho-alkylative vicinal difunctionalization reactions of iodoarenes enabled by palladium–olefin catalysis","authors":"Yu-Xiu Li, Cheng-Hao Zong, Yu Meng, Lei Jiao","doi":"10.1038/s44160-025-00920-6","DOIUrl":"10.1038/s44160-025-00920-6","url":null,"abstract":"Direct access to multifunctionalized arenes through regioselective vicinal difunctionalization of aryl substrates is a challenging yet highly sought-after process. Palladium–norbornene catalysis enables the synthesis of ipso,ortho-difunctionalized products from haloarenes; however, selective mono-ortho-alkylative vicinal difunctionalization reactions of para-substituted haloarene substrates have remained elusive. Here we report the use of a methyl-modified thio-cycloolefin ligand for the palladium-catalysed ortho-alkylative vicinal difunctionalization of para-substituted iodoarenes. This catalytic system demonstrates compatibility with a variety of para-substituted iodoarenes, alkyl iodides and termination reagents, facilitating ortho-alkylative vicinal difunctionalization unattainable by conventional palladium–norbornene catalysis. In addition, the catalytic system can be used for the selective mono-ortho-arylation of para-substituted iodoarenes, enabling the synthesis of triphenylenes. Mechanistic studies reveal the origins of site selectivity within the catalytic process, through isolation of key intermediates and examination of their stoichiometric reactivity. This work highlights the versatility of palladium–olefin catalysis in addressing the complexities associated with constructing multifunctionalized aromatic frameworks through rational molecular design. Palladium–olefin catalysis is utilized to overcome the ‘ortho constraint’ in the Catellani reaction of para-substituted iodoarenes. Using a methyl-modified thio-cycloolefin ligand, this method enables selective mono-alkylative vicinal difunctionalization of para-substituted iodoarenes, which is unattainable by conventional palladium–norbornene catalysis.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 2","pages":"240-250"},"PeriodicalIF":20.0,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145447773","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 : 2025-11-05DOI: 10.1038/s44160-025-00914-4
Xizheng Wang, Ning Liu, Zhennan Huang, Ji Yang, Gang Chen, Boyang Li, Ti Xie, Sean Overa, Alexandra H Brozena, Tangyuan Li, Farhan Mumtaz, Bohong Zhang, Ying Lin, Mingze Li, Bowen Mei, Shuke Li, Jinsong Huang, Jie Huang, Feng Jiao, Cheng Gong, Guofeng Wang, Miaofang Chi, Ichiro Takeuchi, Yiguang Ju, Liangbing Hu
Vapour-phase synthesis methods have shown promise for the scalable synthesis of nanomaterials and coatings. However, the vaporization of different precursors for the synthesis of a broad nanomaterial space, particularly at atmospheric pressure, while maintaining compositional and structural control of the final product is challenging. Here we report the generation of an ultrahigh-temperature atomic vapour at atmospheric pressure based on electrified heating, for the growth of multi-elemental nanomaterials and thin films. This process relies on a reactor design whereby solid-state precursors are vaporized within a semi-confined space beneath an electrified heater that can reach ~3,000 K. The proximity of the heater rapidly breaks down the bonds of metal salt precursors and decomposes them into an atomic vapour that expands into a high-temperature (>2,000 K), highly reactive and high-flux vapour (1021–1022 atoms per cm2 per second) that travels upwards in a directional flow. When mixed with entrained ambient gases, the highly reactive atomic species rapidly nucleate and grow into the desired final products, including alloys, oxides, sulfides and thin films, which can be deposited on a low-temperature substrate. This EVD approach can synthesize a broad range of functional nanomaterials at atmospheric pressure, including single-phase multi-elemental nanomaterials formed under thermodynamically non-equilibrium conditions. Vapour-phase methods are promising for nanomaterial synthesis but the vaporization of different precursors for the synthesis of a broad nanomaterial space is challenging. Here electrified vapour deposition generates ultrahigh-temperature, high-flux atomic vapour at atmospheric pressure to rapidly vaporize diverse precursors, enabling the synthesis of multi-elemental nanomaterials with uniform compositions and tunable structures.
{"title":"Electrified vapour deposition at ultrahigh temperature and atmospheric pressure for nanomaterials synthesis","authors":"Xizheng Wang, Ning Liu, Zhennan Huang, Ji Yang, Gang Chen, Boyang Li, Ti Xie, Sean Overa, Alexandra H Brozena, Tangyuan Li, Farhan Mumtaz, Bohong Zhang, Ying Lin, Mingze Li, Bowen Mei, Shuke Li, Jinsong Huang, Jie Huang, Feng Jiao, Cheng Gong, Guofeng Wang, Miaofang Chi, Ichiro Takeuchi, Yiguang Ju, Liangbing Hu","doi":"10.1038/s44160-025-00914-4","DOIUrl":"10.1038/s44160-025-00914-4","url":null,"abstract":"Vapour-phase synthesis methods have shown promise for the scalable synthesis of nanomaterials and coatings. However, the vaporization of different precursors for the synthesis of a broad nanomaterial space, particularly at atmospheric pressure, while maintaining compositional and structural control of the final product is challenging. Here we report the generation of an ultrahigh-temperature atomic vapour at atmospheric pressure based on electrified heating, for the growth of multi-elemental nanomaterials and thin films. This process relies on a reactor design whereby solid-state precursors are vaporized within a semi-confined space beneath an electrified heater that can reach ~3,000 K. The proximity of the heater rapidly breaks down the bonds of metal salt precursors and decomposes them into an atomic vapour that expands into a high-temperature (>2,000 K), highly reactive and high-flux vapour (1021–1022 atoms per cm2 per second) that travels upwards in a directional flow. When mixed with entrained ambient gases, the highly reactive atomic species rapidly nucleate and grow into the desired final products, including alloys, oxides, sulfides and thin films, which can be deposited on a low-temperature substrate. This EVD approach can synthesize a broad range of functional nanomaterials at atmospheric pressure, including single-phase multi-elemental nanomaterials formed under thermodynamically non-equilibrium conditions. Vapour-phase methods are promising for nanomaterial synthesis but the vaporization of different precursors for the synthesis of a broad nanomaterial space is challenging. Here electrified vapour deposition generates ultrahigh-temperature, high-flux atomic vapour at atmospheric pressure to rapidly vaporize diverse precursors, enabling the synthesis of multi-elemental nanomaterials with uniform compositions and tunable structures.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":"14-26"},"PeriodicalIF":20.0,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145441225","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 : 2025-11-05DOI: 10.1038/s44160-025-00915-3
Chao Li, Xinyao Li, Jiaxing Li, Zhixing Wang, Dunhuang Ouyang, Ning Jiao, Song Song
Pyridine derivatives are one of the most common heterocycles in chemistry. The 3-halopyridines are generally synthesized by indirect methods, including functional group conversion or a temporary dearomatization–rearomatization process. Although the direct electrophilic halogenation of pyridines provides straightforward access to 3-halopyridines, it has been rarely reported owing to the poor π nucleophilicity of pyridines. Here we describe a general direct regioselective C-3 halogenation of pyridines promoted by an ether solvation effect. This radical process enables the regioselective reaction to occur at the C-3 position of pyridines, rather than other aromatic C–H bonds, and can be applied to the late-stage halogenation of complex molecules. The mechanistic studies show that the interaction between the pyridine substrate, ether solvent and haleniums plays a dominant role in the reactivity and regioselectivity. Direct regioselective C-3 halogenation of pyridines is achieved using ether solvents, and interactions between the pyridine substrate, ether solvent and haleniums play a dominant role in the reactivity and regioselectivity. The simple conditions and broad functional group tolerance make this protocol practical for late-stage synthesis and modification of bioactive molecules.
{"title":"Direct regioselective C-3 halogenation of pyridines","authors":"Chao Li, Xinyao Li, Jiaxing Li, Zhixing Wang, Dunhuang Ouyang, Ning Jiao, Song Song","doi":"10.1038/s44160-025-00915-3","DOIUrl":"10.1038/s44160-025-00915-3","url":null,"abstract":"Pyridine derivatives are one of the most common heterocycles in chemistry. The 3-halopyridines are generally synthesized by indirect methods, including functional group conversion or a temporary dearomatization–rearomatization process. Although the direct electrophilic halogenation of pyridines provides straightforward access to 3-halopyridines, it has been rarely reported owing to the poor π nucleophilicity of pyridines. Here we describe a general direct regioselective C-3 halogenation of pyridines promoted by an ether solvation effect. This radical process enables the regioselective reaction to occur at the C-3 position of pyridines, rather than other aromatic C–H bonds, and can be applied to the late-stage halogenation of complex molecules. The mechanistic studies show that the interaction between the pyridine substrate, ether solvent and haleniums plays a dominant role in the reactivity and regioselectivity. Direct regioselective C-3 halogenation of pyridines is achieved using ether solvents, and interactions between the pyridine substrate, ether solvent and haleniums play a dominant role in the reactivity and regioselectivity. The simple conditions and broad functional group tolerance make this protocol practical for late-stage synthesis and modification of bioactive molecules.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":"36-45"},"PeriodicalIF":20.0,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145441226","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 : 2025-10-30DOI: 10.1038/s44160-025-00924-2
Determining the atomic-level structures of confined polymers is challenging. Now, helical polythiophene and polypyrrole are synthesized in situ within a chiral iron-based metal–organic framework (MOF) and resolved by single-crystal X-ray diffraction. The polymers form single-handed helices in the MOF’s narrow channels and amplify its chirality-induced spin selectivity.
{"title":"Synthesis of crystalline helical polymers within metal–organic frameworks","authors":"","doi":"10.1038/s44160-025-00924-2","DOIUrl":"10.1038/s44160-025-00924-2","url":null,"abstract":"Determining the atomic-level structures of confined polymers is challenging. Now, helical polythiophene and polypyrrole are synthesized in situ within a chiral iron-based metal–organic framework (MOF) and resolved by single-crystal X-ray diffraction. The polymers form single-handed helices in the MOF’s narrow channels and amplify its chirality-induced spin selectivity.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 1","pages":"8-9"},"PeriodicalIF":20.0,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145405013","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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