Pub Date : 2025-11-18DOI: 10.1038/s44160-025-00938-w
Su Huang, Daming Zeng, Ming Wang, Xuefeng Jiang
Here Ni-catalysed multicomponent reductive cross-coupling of thiourea dioxide, aziridines and alkyl halides is disclosed, enabling the divergent synthesis of β-amino sulfides and disulfides. The β-amino sulfides are selectively synthesized using a planar bidentate 2,9-dimethyl-1,10-phenanthroline ligand through a NiI/NiIII catalytic cycle. Moreover, the non-planar bidentate ligand 6,6′-dimethyl-2,2′-dipyridyl, possessing an axial torsional dihedral angle, affords β-amino disulfides via a Ni0/NiII/NiI catalytic cycle. Density functional theory calculations demonstrate that the planar bidentate ligand converts the catalytic centre from NiI–SR to a NiIII species via oxidative addition with a monosulfurating transformation, and the non-planar bidentate ligand induces the dimerization of NiI–SR, forming a sulfido-bridged dimer for disulfurating transformations. Clinically applied pharmaceuticals, such as bezafibrate, indometacin and thalidomide, with reactive functional groups, are compatible with the versatile sulfuration linkage, demonstrating the applicability of this strategy. Ni-catalysed multicomponent reductive cross-coupling of aziridines, thiourea dioxide and alkyl halides enables the ligand-controlled synthesis of β-amino sulfides and disulfides. A planar ligand facilitates the oxidative addition of NiI–SR to NiIII for monosulfurating, whereas a non-planar ligand promotes NiI–SR dimerization into a sulfido-bridged species for disulfurating.
{"title":"Ligand-controlled divergent sulfuration and disulfuration via Ni-catalysed reductive cross-coupling involving thiourea dioxide","authors":"Su Huang, Daming Zeng, Ming Wang, Xuefeng Jiang","doi":"10.1038/s44160-025-00938-w","DOIUrl":"10.1038/s44160-025-00938-w","url":null,"abstract":"Here Ni-catalysed multicomponent reductive cross-coupling of thiourea dioxide, aziridines and alkyl halides is disclosed, enabling the divergent synthesis of β-amino sulfides and disulfides. The β-amino sulfides are selectively synthesized using a planar bidentate 2,9-dimethyl-1,10-phenanthroline ligand through a NiI/NiIII catalytic cycle. Moreover, the non-planar bidentate ligand 6,6′-dimethyl-2,2′-dipyridyl, possessing an axial torsional dihedral angle, affords β-amino disulfides via a Ni0/NiII/NiI catalytic cycle. Density functional theory calculations demonstrate that the planar bidentate ligand converts the catalytic centre from NiI–SR to a NiIII species via oxidative addition with a monosulfurating transformation, and the non-planar bidentate ligand induces the dimerization of NiI–SR, forming a sulfido-bridged dimer for disulfurating transformations. Clinically applied pharmaceuticals, such as bezafibrate, indometacin and thalidomide, with reactive functional groups, are compatible with the versatile sulfuration linkage, demonstrating the applicability of this strategy. Ni-catalysed multicomponent reductive cross-coupling of aziridines, thiourea dioxide and alkyl halides enables the ligand-controlled synthesis of β-amino sulfides and disulfides. A planar ligand facilitates the oxidative addition of NiI–SR to NiIII for monosulfurating, whereas a non-planar ligand promotes NiI–SR dimerization into a sulfido-bridged species for disulfurating.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 3","pages":"398-408"},"PeriodicalIF":20.0,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536668","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 : 2025-11-18DOI: 10.1038/s44160-025-00935-z
Daniel Tezze, Covadonga Álvarez-García, Daniel Margineda, Mohammad Furqan, Samuele Mattioni, José Manuel Pereira, Umer Ahsan, Vlastimil Mazanek, Yogesh Kumar Maurya, Ilaria Abdel Aziz, Daniele Mantione, Aurelio Mateo-Alonso, Frederik Schiller, Fèlix Casanova, Samuel Mañas-Valero, Angel Alegria, Eugenio Coronado, Iván Rivilla, Zdenek Sofer, Beatriz Martín-García, Maider Ormaza, Raul Arenal, Luis E. Hueso, Marco Gobbi
The intercalation of molecular species into van der Waals (vdW) crystals is a powerful approach to combine the physical properties of vdW materials with the chemical versatility of molecules. However, its transformative promise remains underexplored, partly due to the difficulty of preserving high crystalline quality down to the few-layer limit using conventional intercalation methods. Here we present a galvanic strategy that exploits the low reduction potentials of selected metals to intercalate diverse molecular cations, including organometallic and chiral species, into both bulk vdW crystals and few-layer flakes under mild conditions, yielding 50 organic–inorganic superlattices. In addition, our method enables vertical intercalation heterostructures, where molecular cations are confined to a single component in a vdW stack, and lateral heterostructures, where two distinct molecular species are introduced into adjacent regions of the same flake. Finally, we demonstrate device-level integration of superconducting heterostructures, highlighting the prospects of galvanic intercalation for hybrid devices and emergent quantum phenomena. A galvanic strategy enables the intercalation of diverse molecular cations into bulk and few-layer van der Waals crystals under mild conditions, yielding 50 organic–inorganic superlattices. This method enables the definition of vertical and lateral intercalation heterostructures, opening avenues for the device integration of hybrid quantum materials.
{"title":"Galvanic intercalation of molecular cations into van der Waals materials and heterostructures","authors":"Daniel Tezze, Covadonga Álvarez-García, Daniel Margineda, Mohammad Furqan, Samuele Mattioni, José Manuel Pereira, Umer Ahsan, Vlastimil Mazanek, Yogesh Kumar Maurya, Ilaria Abdel Aziz, Daniele Mantione, Aurelio Mateo-Alonso, Frederik Schiller, Fèlix Casanova, Samuel Mañas-Valero, Angel Alegria, Eugenio Coronado, Iván Rivilla, Zdenek Sofer, Beatriz Martín-García, Maider Ormaza, Raul Arenal, Luis E. Hueso, Marco Gobbi","doi":"10.1038/s44160-025-00935-z","DOIUrl":"10.1038/s44160-025-00935-z","url":null,"abstract":"The intercalation of molecular species into van der Waals (vdW) crystals is a powerful approach to combine the physical properties of vdW materials with the chemical versatility of molecules. However, its transformative promise remains underexplored, partly due to the difficulty of preserving high crystalline quality down to the few-layer limit using conventional intercalation methods. Here we present a galvanic strategy that exploits the low reduction potentials of selected metals to intercalate diverse molecular cations, including organometallic and chiral species, into both bulk vdW crystals and few-layer flakes under mild conditions, yielding 50 organic–inorganic superlattices. In addition, our method enables vertical intercalation heterostructures, where molecular cations are confined to a single component in a vdW stack, and lateral heterostructures, where two distinct molecular species are introduced into adjacent regions of the same flake. Finally, we demonstrate device-level integration of superconducting heterostructures, highlighting the prospects of galvanic intercalation for hybrid devices and emergent quantum phenomena. A galvanic strategy enables the intercalation of diverse molecular cations into bulk and few-layer van der Waals crystals under mild conditions, yielding 50 organic–inorganic superlattices. This method enables the definition of vertical and lateral intercalation heterostructures, opening avenues for the device integration of hybrid quantum materials.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 3","pages":"388-397"},"PeriodicalIF":20.0,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145536669","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 : 2025-11-13DOI: 10.1038/s44160-025-00930-4
Ye Yang, André Knapp, David Bodesheim, Alexander Croy, Mike Hambsch, Ilka Hermes, Chandrasekhar Naisa, Darius Pohl, Bernd Rellinghaus, Changsheng Zhao, Stefan C. B. Mannsfeld, Gianaurelio Cuniberti, Zhiyong Wang, Renhao Dong, Andreas Fery, Xinliang Feng
Two-dimensional polymers (2DPs), comprising mono- or multilayer covalent polymeric networks with long-range order in two orthogonal directions, are of considerable interest due to their unique physicochemical properties. However, achieving precise thickness control from monolayer to bilayer, crucial for exploring proximity effect-driven phenomena beyond the monolayer limit, remains synthetically challenging. Here we report the on-water surface synthesis of crystalline mechanically interlocked monolayer and bilayer 2DP (MI-M2DP and MI-B2DP) films by embedding macrocyclic molecules with one and two cavities into 2DP backbones. The incorporation of bulky macrocyclic molecules introduces periodic mechanical bonds that precisely control interlayer interlocking, enabling selective monolayer or bilayer 2DP formation. Both MI-M2DP and MI-B2DP exhibit homogeneous, large-area films with ordered hexagonal pores and high modulus. MI-B2DP demonstrates an exceptionally high effective Young’s modulus of 151 ± 16 GPa (indentation method), surpassing MI-M2DP (90 ± 14 GPa), van der Waals-stacked MI-M2DPs (46 ± 11 GPa) and other reported multilayer 2DPs (<50 GPa). Modelling confirms that the mechanical interlocking minimizes interlayer sliding and reinforces the structure. Mechanically interlocked monolayer and bilayer two-dimensional polymers (2DPs) are synthesized on the water surface by embedding macrocyclic molecules with one and two cavities into the backbones. The resulting bilayer 2DP displays a high effective Young’s modulus, exceeding other reported multilayer 2DPs.
二维聚合物（2DPs），由单层或多层共价聚合物网络组成，在两个正交方向上具有长程有序，由于其独特的物理化学性质而引起了相当大的兴趣。然而，实现从单层到双层的精确厚度控制，对于探索超越单层极限的接近效应驱动现象至关重要，在合成上仍然具有挑战性。在这里，我们报道了通过在2DP骨架中嵌入具有一个和两个空腔的大环分子，在水表面合成晶体机械互锁单层和双层2DP （MI-M2DP和MI-B2DP）薄膜。庞大的大环分子的结合引入了周期性的机械键，精确地控制层间联锁，使选择性单层或双层2DP形成。MI-M2DP和MI-B2DP均表现出均匀、大面积的薄膜，具有有序的六方孔和高模量。MI-B2DP的有效杨氏模量高达151±16 GPa（压痕法），超过了MI-M2DP（90±14 GPa）、van der waals堆叠MI-M2DP（46±11 GPa）和其他已报道的多层2dp （50 GPa）。模型证实，机械联锁最小化层间滑动和加强结构。
{"title":"Mechanically interlocked monolayer and bilayer two-dimensional polymers with high elastic modulus","authors":"Ye Yang, André Knapp, David Bodesheim, Alexander Croy, Mike Hambsch, Ilka Hermes, Chandrasekhar Naisa, Darius Pohl, Bernd Rellinghaus, Changsheng Zhao, Stefan C. B. Mannsfeld, Gianaurelio Cuniberti, Zhiyong Wang, Renhao Dong, Andreas Fery, Xinliang Feng","doi":"10.1038/s44160-025-00930-4","DOIUrl":"10.1038/s44160-025-00930-4","url":null,"abstract":"Two-dimensional polymers (2DPs), comprising mono- or multilayer covalent polymeric networks with long-range order in two orthogonal directions, are of considerable interest due to their unique physicochemical properties. However, achieving precise thickness control from monolayer to bilayer, crucial for exploring proximity effect-driven phenomena beyond the monolayer limit, remains synthetically challenging. Here we report the on-water surface synthesis of crystalline mechanically interlocked monolayer and bilayer 2DP (MI-M2DP and MI-B2DP) films by embedding macrocyclic molecules with one and two cavities into 2DP backbones. The incorporation of bulky macrocyclic molecules introduces periodic mechanical bonds that precisely control interlayer interlocking, enabling selective monolayer or bilayer 2DP formation. Both MI-M2DP and MI-B2DP exhibit homogeneous, large-area films with ordered hexagonal pores and high modulus. MI-B2DP demonstrates an exceptionally high effective Young’s modulus of 151 ± 16 GPa (indentation method), surpassing MI-M2DP (90 ± 14 GPa), van der Waals-stacked MI-M2DPs (46 ± 11 GPa) and other reported multilayer 2DPs (<50 GPa). Modelling confirms that the mechanical interlocking minimizes interlayer sliding and reinforces the structure. Mechanically interlocked monolayer and bilayer two-dimensional polymers (2DPs) are synthesized on the water surface by embedding macrocyclic molecules with one and two cavities into the backbones. The resulting bilayer 2DP displays a high effective Young’s modulus, exceeding other reported multilayer 2DPs.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 3","pages":"357-366"},"PeriodicalIF":20.0,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00930-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145498918","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 : 2025-11-13DOI: 10.1038/s44160-025-00943-z
Precisely controlling the thickness of two-dimensional polymers (2DPs) is challenging. Now, crystalline monolayer and bilayer 2DPs are synthesized by embedding macrocyclic molecules in the polymer backbones to form mechanical bonds and provide control over the number of layers. This mechanical interlocking endows the synthetic bilayer with a high Young’s modulus.
{"title":"Controlled synthesis of monolayer and bilayer two-dimensional polymers","authors":"","doi":"10.1038/s44160-025-00943-z","DOIUrl":"10.1038/s44160-025-00943-z","url":null,"abstract":"Precisely controlling the thickness of two-dimensional polymers (2DPs) is challenging. Now, crystalline monolayer and bilayer 2DPs are synthesized by embedding macrocyclic molecules in the polymer backbones to form mechanical bonds and provide control over the number of layers. This mechanical interlocking endows the synthetic bilayer with a high Young’s modulus.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 3","pages":"319-320"},"PeriodicalIF":20.0,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145498915","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}
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 : 2025-11-12DOI: 10.1038/s44160-025-00933-1
Jian Sheng, Yifan Xu, Zhen Han, Sida Sun, Xinrui Zhang, Chi Xu, Runze Lai, Dan-Na Wu, Hai-Gang Lu, Si-Dian Li, Yan Li
Rapid Joule heating (RJH) has emerged as a transformative technique for ultrafast materials synthesis, attributed to extreme thermal conditions, fast reaction speed and high energy efficiency. Here, to improve the controllability and versatility of RJH, we introduce nanocatalysts and establish a catalytic RJH process that combines the precision of vapour–liquid–solid (VLS) growth processes with the ultrafast kinetics of Joule heating, enabling structurally controlled synthesis of one-dimensional (1D) nanomaterials within seconds. We verify the validity of VLS mechanism at temperatures beyond 2,500 °C under RJH, in which the far-from-equilibrium reaction conditions further enhance the growth and diameter control of 1D nanomaterials. Consequently, nanowires of refractory carbides, II–VI/III–V group semiconductors, high-entropy carbides, and multiwalled and single-walled carbon nanotubes are synthesized, showing the generality of the RJH-VLS strategy. With demonstrated scalability to the 10-g scale, low energy consumption on the order of tens of kilojoules per gram, and the ability to precisely control morphology through nanocatalysts, this catalytic RJH strategy shows great promise for the synthesis and production of 1D materials. A catalytic Joule heating approach is developed for the growth of one-dimensional nanomaterials via a vapour–liquid–solid mechanism under far-from-equilibrium reaction conditions. It demonstrates broad applicability for the rapid and energy-efficient synthesis of diverse nanowires and nanotubes, including refractory and high-entropy systems.
{"title":"Catalytic Joule heating synthesis of one-dimensional nanomaterials in seconds","authors":"Jian Sheng, Yifan Xu, Zhen Han, Sida Sun, Xinrui Zhang, Chi Xu, Runze Lai, Dan-Na Wu, Hai-Gang Lu, Si-Dian Li, Yan Li","doi":"10.1038/s44160-025-00933-1","DOIUrl":"10.1038/s44160-025-00933-1","url":null,"abstract":"Rapid Joule heating (RJH) has emerged as a transformative technique for ultrafast materials synthesis, attributed to extreme thermal conditions, fast reaction speed and high energy efficiency. Here, to improve the controllability and versatility of RJH, we introduce nanocatalysts and establish a catalytic RJH process that combines the precision of vapour–liquid–solid (VLS) growth processes with the ultrafast kinetics of Joule heating, enabling structurally controlled synthesis of one-dimensional (1D) nanomaterials within seconds. We verify the validity of VLS mechanism at temperatures beyond 2,500 °C under RJH, in which the far-from-equilibrium reaction conditions further enhance the growth and diameter control of 1D nanomaterials. Consequently, nanowires of refractory carbides, II–VI/III–V group semiconductors, high-entropy carbides, and multiwalled and single-walled carbon nanotubes are synthesized, showing the generality of the RJH-VLS strategy. With demonstrated scalability to the 10-g scale, low energy consumption on the order of tens of kilojoules per gram, and the ability to precisely control morphology through nanocatalysts, this catalytic RJH strategy shows great promise for the synthesis and production of 1D materials. A catalytic Joule heating approach is developed for the growth of one-dimensional nanomaterials via a vapour–liquid–solid mechanism under far-from-equilibrium reaction conditions. It demonstrates broad applicability for the rapid and energy-efficient synthesis of diverse nanowires and nanotubes, including refractory and high-entropy systems.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 3","pages":"367-376"},"PeriodicalIF":20.0,"publicationDate":"2025-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145492601","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
The editing of organic molecules through single-atom modification is an enabling capability for medicinal chemistry. Although several examples of single-atom insertions into the carbon–carbon double bonds of unsaturated aromatic ring systems have been reported, heteroatom insertions into chemically inert carbon–carbon single bonds are comparatively rare. Here we report a photochemical strategy for the formal migration of oxygen atoms into carbon–carbon single bonds. This protocol is based on the ability of copper(II) salts to induce photochemical homolytic cleavage of carbon–carbon bonds adjacent to alcohols and to mediate oxidative coupling reactions of the resulting organoradical intermediates. Application of this method to cyclic alcohol substrates results in oxygen atom insertions into saturated carbocyclic rings, and its extension to linear alcohol substrates enables atomic permutation of hydroxymethyl functionalities into methyl ethers. Heteroatom insertions into chemically inert carbon–carbon single bonds are rare compared to their unsaturated analogues. Now, ligand-to-metal charge transfer offers a promising entry point for oxygen atom insertion into saturated carbocyclic scaffolds.
{"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":"10.1038/s44160-025-00937-x","url":null,"abstract":"The editing of organic molecules through single-atom modification is an enabling capability for medicinal chemistry. Although several examples of single-atom insertions into the carbon–carbon double bonds of unsaturated aromatic ring systems have been reported, heteroatom insertions into chemically inert carbon–carbon single bonds are comparatively rare. Here we report a photochemical strategy for the formal migration of oxygen atoms into carbon–carbon single bonds. This protocol is based on the ability of copper(II) salts to induce photochemical homolytic cleavage of carbon–carbon bonds adjacent to alcohols and to mediate oxidative coupling reactions of the resulting organoradical intermediates. Application of this method to cyclic alcohol substrates results in oxygen atom insertions into saturated carbocyclic rings, and its extension to linear alcohol substrates enables atomic permutation of hydroxymethyl functionalities into methyl ethers. Heteroatom insertions into chemically inert carbon–carbon single bonds are rare compared to their unsaturated analogues. Now, ligand-to-metal charge transfer offers a promising entry point for oxygen atom insertion into saturated carbocyclic scaffolds.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"5 3","pages":"349-356"},"PeriodicalIF":20.0,"publicationDate":"2025-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00937-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145478209","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}
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}
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