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Toward a Taxol-producing microbial cell factory 迈向生产紫杉醇的微生物细胞工厂
IF 2
Nature synthesis Pub Date : 2025-04-30 DOI: 10.1038/s44160-025-00801-y
Vincent Courdavault, Nicolas Papon
{"title":"Toward a Taxol-producing microbial cell factory","authors":"Vincent Courdavault, Nicolas Papon","doi":"10.1038/s44160-025-00801-y","DOIUrl":"10.1038/s44160-025-00801-y","url":null,"abstract":"Reconstruction of the late enzymatic steps of the yew Taxol biosynthetic pathway in yeast enables the bioproduction of Taxol.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 10","pages":"1175-1177"},"PeriodicalIF":20.0,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256867","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}
引用次数: 0
Reactions of a Zn–Zn bond with main group carbene analogues as a prototypical case of reductive addition Zn-Zn键与主基团碳类似物的反应为还原性加成的典型案例。
IF 2
Nature synthesis Pub Date : 2025-04-29 DOI: 10.1038/s44160-025-00790-y
Wenbang Yang, Andrew J. P. White, Mark R. Crimmin
{"title":"Reactions of a Zn–Zn bond with main group carbene analogues as a prototypical case of reductive addition","authors":"Wenbang Yang, Andrew J. P. White, Mark R. Crimmin","doi":"10.1038/s44160-025-00790-y","DOIUrl":"10.1038/s44160-025-00790-y","url":null,"abstract":"Oxidative addition most commonly involves the addition of a substrate to a metal centre. This reaction is fundamental across synthetic chemistry and underpins numerous catalytic methods. In the textbook description of oxidative addition reactions, a net increase in the formal oxidation state of the metal occurs with simultaneous bond breaking at the substrate. The majority of known oxidative addition reactions, however, involve substrates bearing relatively electronegative elements (for example, hydrogen, carbon, nitrogen, oxygen and halogens) and there has been little discussion of how addition processes may fundamentally change if substrates were constructed from more electropositive elements. Here we show that the zinc–zinc bonded complex, Cp*ZnZnCp* (Cp* = pentamethylcyclopentadienyl), which is isoelectronic with dihydrogen, undergoes facile addition to the metal (or semi-metal) centres of a series of main group carbene analogues based on silicon, aluminium, gallium or indium. Reactions proceed with complete breaking of the zinc–zinc bond and an increase in the coordination number of the central metal from two to four. Our analysis suggests that these addition processes are not oxidative, but rather there is likely a continuum of redox outcomes spanning oxidative, redox neutral and reductive. The addition of Cp*ZnZnCp* to silicon(II) provides the most compelling case for a prototypical reductive addition process. The zinc–zinc bonded complex, Cp*ZnZnCp* (Cp* = pentamethylcyclopentadienyl), undergoes facile addition to the metal (or semi-metal) centres of a series of main group carbene analogues based on silicon, aluminium, gallium or indium. The addition of Cp*ZnZnCp* to silicon(II) provides a compelling case for a prototypical reductive addition process.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 8","pages":"995-1000"},"PeriodicalIF":20.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12334357/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144818578","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}
引用次数: 0
Synthesis of a lattice-resolved laminate-structured perovskite heterointerface 晶格分解层状结构钙钛矿异质界面的合成
IF 2
Nature synthesis Pub Date : 2025-04-29 DOI: 10.1038/s44160-025-00787-7
Zhimin Li, Pengfei Guo, Yalan Zhang, Weizhen Wang, Songhua Cai, Yuanyuan Zhou
{"title":"Synthesis of a lattice-resolved laminate-structured perovskite heterointerface","authors":"Zhimin Li, Pengfei Guo, Yalan Zhang, Weizhen Wang, Songhua Cai, Yuanyuan Zhou","doi":"10.1038/s44160-025-00787-7","DOIUrl":"10.1038/s44160-025-00787-7","url":null,"abstract":"Two-dimensional surface passivation has been shown to be useful for achieving state-of-the-art perovskite optoelectronics, and the microstructural and phase heterogeneities of two-dimensional perovskite passivators can influence their roles. However, the synthesis of co-homogenized, stable microstructure and phase in such passivators remains challenging. Herein we leverage a [6,6]-phenyl-C61-butyric acid methyl ester molecular interlayer to mediate the reaction of the two-dimensional passivator and perovskite, leading to a uniform purer-phase two-dimensional perovskite capping layer. This interlayer mitigates the grain-boundary etching encountered in conventional approaches, creating molecular passivation directly onto the perovskite surface. The inverted perovskite solar cells made with the interlayer feature a laminate-structured perovskite heterointerface at the electron-extracting side, which contributes to improved charge energetics and film stability, owing to the regulated band alignment and laminate-layer protection, respectively. Power conversion efficiencies up to 25.97% are achieved, together with enhanced device stabilities under protocols standardized by the International Summit on Organic Photovoltaic Stability, showing T90 lifetimes (the time at which they maintain 90% of their efficiency) of over 1,000 h in both the damp-heat test (85 °C, 85% relative humidity) and maximum power point tracking under one-sun illumination. Lattice-resolved insights are provided to link the microstructure to device performance, shedding light on the significance of passivator-microstructure uniformity and reliability on the performance of perovskite optoelectronics. A method mediated by [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is developed to synthesize a uniform, purer-phase 2D perovskite capping layer on 3D perovskite films. The PCBM interlayer mediates the reaction of the 2D passivator with the 3D perovskite and prevents grain-boundary etching, enhancing solar cell efficiency and stability.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 9","pages":"1078-1087"},"PeriodicalIF":20.0,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123644","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}
引用次数: 0
Iron-catalysed radical Markovnikov hydroamidation of complex alkenes 铁催化的络合烯烃自由基马尔可夫尼科夫氢酰胺化反应
IF 2
Nature synthesis Pub Date : 2025-04-17 DOI: 10.1038/s44160-025-00792-w
Mengjun Huang, Constantin Gabriel Daniliuc, Armido Studer
{"title":"Iron-catalysed radical Markovnikov hydroamidation of complex alkenes","authors":"Mengjun Huang, Constantin Gabriel Daniliuc, Armido Studer","doi":"10.1038/s44160-025-00792-w","DOIUrl":"10.1038/s44160-025-00792-w","url":null,"abstract":"Nitrogen atoms are integral components of various chemical functional groups, including amines, amides and N-heterocycles, among others. Consequently, they play an important role in pharmaceuticals, agrochemicals, natural products, materials and commodity chemicals. The formation of C–N bonds is reliably achieved through methods, such as reductive amination, N-alkylation and cross-coupling. Hydroamination, starting with alkenes, presents a valuable alternative for accessing organic compounds containing nitrogen, as alkenes are highly abundant. Here we present a method for the iron-catalysed radical hydroamidation of alkenes. To this end, we developed a radical amidation reagent that can be readily prepared on a large scale, facilitating the efficient transfer of the synthetically valuable cyanamide functionality across both activated and unactivated double bonds. The scope of the reaction is remarkably broad, demonstrating its applicability to the diastereoselective hydroamidation of complex terpene natural products. Importantly, the synthesis of 15N-labelled amines is possible using this strategy. Subsequent chemistry, converting the distinctive cyanamide functionality into other useful groups, further validates the value of the developed methodology. An iron-catalysed radical Markovnikov hydroamidation of alkenes using a cyanamide reagent is reported. The method achieves C–N bond formation with high yields and selectivity and is applicable to a wide range of alkenes and natural products. The cyanamide functionality can be transformed into various functional groups, highlighting its potential for advanced applications in natural product synthesis.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 8","pages":"1001-1008"},"PeriodicalIF":20.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00792-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123618","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}
引用次数: 0
Encapsulated halide perovskites 封装卤化物钙钛矿
IF 2
Nature synthesis Pub Date : 2025-04-17 DOI: 10.1038/s44160-025-00802-x
Jeremy Sloan
{"title":"Encapsulated halide perovskites","authors":"Jeremy Sloan","doi":"10.1038/s44160-025-00802-x","DOIUrl":"10.1038/s44160-025-00802-x","url":null,"abstract":"Forming halide perovskites inside carbon nanotubes chemically protects them, enabling their application as highly efficient X-ray detectors with low dark current.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 9","pages":"1025-1026"},"PeriodicalIF":20.0,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123698","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}
引用次数: 0
Synthesis of a crystalline two-dimensional [c2]daisy chain honeycomb network 结晶二维[c2]菊花链蜂窝网络的合成
IF 2
Nature synthesis Pub Date : 2025-04-15 DOI: 10.1038/s44160-025-00791-x
Zheng-Bin Tang, Lifang Bian, Xiaohe Miao, Helei Gao, Lin Liu, Qike Jiang, Dengke Shen, Lijun Xu, Andrew C.-H. Sue, Xiaorui Zheng, Zhichang Liu
{"title":"Synthesis of a crystalline two-dimensional [c2]daisy chain honeycomb network","authors":"Zheng-Bin Tang, Lifang Bian, Xiaohe Miao, Helei Gao, Lin Liu, Qike Jiang, Dengke Shen, Lijun Xu, Andrew C.-H. Sue, Xiaorui Zheng, Zhichang Liu","doi":"10.1038/s44160-025-00791-x","DOIUrl":"10.1038/s44160-025-00791-x","url":null,"abstract":"Molecular daisy chains are mechanically bonded materials with unique properties and compelling structures. Despite the exploration of numerous daisy chain structures, the synthesis of a crystalline mechanically interlocked polymer comprising daisy chain units remains elusive because flexible linkers typically yield amorphous gels, while rigid structures lack processability. Here we combine supramolecular crystallization preorganization with post-insertion of mechanical bonds to address this limitation. We use a C3-symmetric tritopic monomer with ammonium moieties and oligoether arms to generate a preorganized supramolecular honeycomb-like crystalline network via complementary non-covalent interactions, in an aqueous environment. Subsequently, single-crystal-to-single-crystal transformation-directed thiol–ene click chemistry crosslinks terminal alkenes at the end of the oligoether arms using 1,2-ethanedithiol, covalently locking [c2]daisy chain linkages while preserving long-range order. This two-dimensional mechanically interlocked polymer can be exfoliated from its crystals to generate a multilayer counterpart exhibiting a 47-fold stiffness enhancement relative to its bulk parent. Moreover, the trilayer nanosheets preserve the structural integrity with the same hexagonal symmetry as the bulk parent. Our method enables the synthesis of a single-crystalline two-dimensional mechanically interlocked polymer from flexible monomers with precise synthetic control and unlocks the potential of developing mechanically interlocked materials. A purely organic crystalline two-dimensional mechanically interlocked polymer comprising [c2]daisy chain units forms via preorganized crystallization and thiol–ene click chemistry. This polymer network can be exfoliated to give nanosheets with a 47-fold stiffness enhancement relative to the bulk parent.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 8","pages":"922-930"},"PeriodicalIF":20.0,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123278","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}
引用次数: 0
Stereoconvergent reduction of alkenes using a repurposed iron-based dioxygenase 利用改造的铁基双加氧酶进行烯烃的立体聚合还原
IF 2
Nature synthesis Pub Date : 2025-04-14 DOI: 10.1038/s44160-025-00788-6
Zicong Wan, Xuan Zhang, Helin Zhuang, Zhekai Xie, Lu Yu, Zihang Fu, Yang Sun, Wei Wang, Ruibo Wu, Pengfei Ji
{"title":"Stereoconvergent reduction of alkenes using a repurposed iron-based dioxygenase","authors":"Zicong Wan, Xuan Zhang, Helin Zhuang, Zhekai Xie, Lu Yu, Zihang Fu, Yang Sun, Wei Wang, Ruibo Wu, Pengfei Ji","doi":"10.1038/s44160-025-00788-6","DOIUrl":"10.1038/s44160-025-00788-6","url":null,"abstract":"The stereoconvergent reduction of alkenes for efficient synthesis of chiral compounds is a challenge in synthetic chemistry, even for exquisite enzymes in nature. Natural ene-reductases for example generally catalyse the reduction of alkenes in an enantiodivergent or resolution fashion. Here we report the repurposing of non-haem iron-based dioxygenases to catalyse the stereoconvergent reduction of alkenes through an iron hydride intermediate, by introducing silanes to the biocatalytic system. Directed evolution of gentisate 1,2-dioxygenase led to iron-based ene-reductases with high efficiency (up to 99% yield), excellent enantioselectivity (23 examples with >99% e.e.) and compatibility with a structurally diverse range of substrates. Experimental studies suggest the formation of iron hydride species in the enzyme and support the divalency of iron during the catalytic process. Computational studies show that the reaction is energetically feasible through an iron hydride mechanism and reveal the molecular mechanism of stereoconvergence. A repurposed non-haem, iron-based dioxygenase enables the stereoconvergent reduction of alkenes with excellent selectivity. Mechanistic studies support an iron hydride pathway and reveal the molecular mechanism of stereoconvergence.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 8","pages":"976-986"},"PeriodicalIF":20.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123275","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}
引用次数: 0
A compact catenane with tuneable mechanical chirality 具有可调机械手性的紧凑链烷
IF 2
Nature synthesis Pub Date : 2025-04-14 DOI: 10.1038/s44160-025-00781-z
Chun Tang, Ruihua Zhang, Sultan Almunif, Partha Jyoti Das, Paige J. Brown, Ryan M. Young, Guangcheng Wu, Han Han, Xueze Zhao, Arthur H. G. David, Huang Wu, Bo Song, Alexandre Abhervé, Yong Wu, Yu-Meng Ye, Yuanning Feng, Aspen X.-Y. Chen, Charlotte L. Stern, Zhi Li, Evan A. Scott, Michael R. Wasielewski, J. Fraser Stoddart
{"title":"A compact catenane with tuneable mechanical chirality","authors":"Chun Tang, Ruihua Zhang, Sultan Almunif, Partha Jyoti Das, Paige J. Brown, Ryan M. Young, Guangcheng Wu, Han Han, Xueze Zhao, Arthur H. G. David, Huang Wu, Bo Song, Alexandre Abhervé, Yong Wu, Yu-Meng Ye, Yuanning Feng, Aspen X.-Y. Chen, Charlotte L. Stern, Zhi Li, Evan A. Scott, Michael R. Wasielewski, J. Fraser Stoddart","doi":"10.1038/s44160-025-00781-z","DOIUrl":"10.1038/s44160-025-00781-z","url":null,"abstract":"Catenanes are formed by the mechanical interlocking of two or more rings. Enantiomers of a catenane can exist even if the rings themselves are achiral. Here we demonstrate that two achiral rings, each featuring a polarized cavity and two mirror planes, in addition to a two-fold axis of symmetry, can form a catenane with mechanical chirality. The catenane has been designed using an isostructural desymmetrization strategy, enabling the catenane to adopt a compact co-conformation similar to that of its achiral isostructural counterpart. Mechanical chirality in the catenane occurs when its two rings become interlocked in the compact co-conformation, leading to the loss of the two planes of symmetry present in its individual rings. The resulting enantiomers, which both have two-fold axes of symmetry, exist as a racemic modification in the solid state. Dynamic 1H NMR spectroscopy carried out in acetonitrile-d3 reveals a barrier of 16.4 kcal mol−1 to racemization between the two enantiomeric catenanes, the equilibrium of which can be influenced by the addition of chiral disulfonate anions, which support induced chirality and exhibit optical activity. One of the salts crystallizes to give only one diastereoisomer in the solid state. This research highlights the potential of using the isostructural desymmetrization strategy to create and study mechanical chirality along with its properties. Catenanes can exhibit chirality even when their component rings are achiral. Here an isostructural desymmetrization strategy is developed, demonstrating that two achiral rings, each featuring two mirror planes and a two-fold axis of symmetry, can form a catenane with tuneable mechanical chirality.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 8","pages":"956-964"},"PeriodicalIF":20.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123297","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}
引用次数: 0
Synthesis of single-unit-cell-thick perovskites by liquid-phase confined assembly for high-performance ultrastable X-ray detectors 高性能超稳定x射线探测器用液相限制组装法制备单单元电池厚钙钛矿
IF 2
Nature synthesis Pub Date : 2025-04-14 DOI: 10.1038/s44160-025-00785-9
Meihui Song, Bo Zhao, Bowen Li, Kun Wang, Yulong Jiang, Guodong Jia, Xin Zhao, Boyuan Yu, Yunlong Li, Feng Yang
{"title":"Synthesis of single-unit-cell-thick perovskites by liquid-phase confined assembly for high-performance ultrastable X-ray detectors","authors":"Meihui Song, Bo Zhao, Bowen Li, Kun Wang, Yulong Jiang, Guodong Jia, Xin Zhao, Boyuan Yu, Yunlong Li, Feng Yang","doi":"10.1038/s44160-025-00785-9","DOIUrl":"10.1038/s44160-025-00785-9","url":null,"abstract":"The instability of halide perovskites under working conditions or during complex postprocessing is challenging for practical applications. Here we developed a room-temperature, two-phase assembling strategy to synthesize single-unit-cell perovskite chains within single-walled carbon nanotubes (SWCNTs). This approach is efficient, scalable and tailorable, and can be used to assemble a range of single-chain perovskites. The single-unit-cell-chain perovskites show unconventional stoichiometries (such as [Cs4PbI5]+) due to dimensionality reduction and are balanced by negatively charged nanotubes. A direct X-ray detector constructed with high-entropy-Cs3MCl6@SWCNT exhibits outstanding performance, with a high sensitivity of $$1.22times10^{4},upmu{mathrm{C}},{mathrm{Gy}}_{mathrm{air}}^{-1},{mathrm{cm}}^{-2}$$ , a low dark current density of 0.2 nA cm−2, a negligible dark current drift of 8.5 × 10−7 nA cm−1 s−1 V−1 and a superior detection limit of 16.6 nGyair s−1. These surpass various common semiconductor and state-of-the-art perovskite detectors due to the ionic character of perovskite@SWCNT inducing a strong cation–π interaction, suppressing ion migration. The device is stable under harsh conditions, including continuous X-ray irradiation, high temperatures, exposure to ambient air for 91 days and immersion for 96 h in water. This low-cost synthetic methodology paves the way for the commercialization of potential perovskite X-ray detectors for medical and industrial applications. A two-phase assembly approach is developed to synthesize single-unit-cell-thick perovskite chains within single-walled carbon nanotubes. A direct X-ray detector constructed with the confined perovskite chains exhibits outstanding performance and ultrahigh stability under harsh conditions.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 9","pages":"1056-1067"},"PeriodicalIF":20.0,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123694","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}
引用次数: 0
On-surface synthesis and characterization of linear and cyclic C6 线性和环状C6的表面合成与表征
IF 2
Nature synthesis Pub Date : 2025-04-11 DOI: 10.1038/s44160-025-00784-w
Luye Sun, Yuan Guo, Wenzhi Xiang, Wei Xu
{"title":"On-surface synthesis and characterization of linear and cyclic C6","authors":"Luye Sun, Yuan Guo, Wenzhi Xiang, Wei Xu","doi":"10.1038/s44160-025-00784-w","DOIUrl":"10.1038/s44160-025-00784-w","url":null,"abstract":"Cyclo[n]carbons, belonging to carbon clusters (Cn), have attracted substantial attention from both experimentalists and theoreticians because of their chemical structures and the controversial stabilities of their different isomers. Recently, C26, C20, C18, C16, C14, C13, C12 and C10 have been synthesized and characterized on thin insulating NaCl surfaces. However, synthesis of smaller cyclocarbons (n < 10) remains challenging due to their inherent high reactivity and increased strain. In particular, C6 has been a subject of long-standing theoretical debate because the energy difference between its linear and cyclic forms is very small. Here we successfully generate both linear and cyclic C6 by modulating the thickness of NaCl layers deposited on a Au(111) surface, using tip-induced dehalogenation of hexaiodobenzene (C6I6) molecules at 4.7 K. The linear C6 was generated on 1-monolayer (1-ML) or 2-ML NaCl surfaces and identified as a polyynic structure through bond-resolved atomic force microscopy, verifying the theoretical calculations of a Peierls transition for linear C6 from gas phase to on-surface adsorption. Meanwhile, cyclic C6 could be generated on a 2-ML NaCl surface and its cumulenic nature is confirmed both experimentally and theoretically. Additionally, voltage pulses can induce cyclic C6 to undergo either an adsorption configuration transformation from a nearly planar to a tilted geometry, or a structural transformation to the linear form. Linear C6 and its isomer, cyclic C6 (the smallest aromatic cyclocarbon), are successfully generated on NaCl surfaces by tip-induced dehalogenation of hexaiodobenzene molecules at 4.7 K, and their polyynic and cumulenic structures, respectively, are characterized by bond-resolved atomic force microscopy.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 8","pages":"940-946"},"PeriodicalIF":20.0,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123293","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}
引用次数: 0
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