Nature chemistry最新文献_第9页

Inverted metal-free active template synthesis of rotaxanes via axle‑mediated macrocyclization 轴介导大环化倒立无金属活性模板合成轮烷。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-29 DOI: 10.1038/s41557-026-02188-5

Jiankang Zhong, Axel Troncossi, Enzo Olivieri, Emily Cramp, Chuan Gao, Patrick Zwick, George F. S. Whitehead, David A. Leigh

{"title":"Inverted metal-free active template synthesis of rotaxanes via axle‑mediated macrocyclization","authors":"Jiankang Zhong, Axel Troncossi, Enzo Olivieri, Emily Cramp, Chuan Gao, Patrick Zwick, George F. S. Whitehead, David A. Leigh","doi":"10.1038/s41557-026-02188-5","DOIUrl":"10.1038/s41557-026-02188-5","url":null,"abstract":"Rotaxane synthesis generally requires the macrocycle to contain recognition sites for the threaded axle or its building blocks. Here we show that flexible oligo(ethylene glycol) axles can instead promote the formation of macrocycles around themselves, enabling an inverted, metal-free active-template route to rotaxanes from simple building blocks. The axle accelerates amide-bond-forming macrocyclization through hydrogen bonding, giving [2]rotaxanes in up to 70% yield. Longer axles enable the iterative assembly of higher-order [n]rotaxanes, with up to four macrocycles threaded onto an octa(ethylene glycol) chain. The X-ray crystal structure of such a [5]rotaxane reveals a crowded helical stack of rings stabilized by aromatic stacking and hydrogen bonding, explaining the enhanced efficacy of the later macrocyclizations. Subsequent deletion of the newly formed amides gives structurally minimalist rotaxanes comprising an oligo(ethylene glycol) axle threaded through a cyclohydrocarbon. Removing the requirement for particular functional groups and structural motifs in rotaxane macrocycles increases the accessible structures of mechanically interlocked molecules. Rotaxane assembly by active template synthesis has so far relied on specialized rings to trap the threaded axle. Now it has been shown that oligo(ethylene glycol) chains can accelerate ester aminolysis macrocyclization around themselves, producing [2]rotaxanes without requiring template sites within the ring. Iteration of this process efficiently yields higher-order rotaxanes.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 9","pages":"1658-1668"},"PeriodicalIF":24.5,"publicationDate":"2026-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41557-026-02188-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148352652","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Covalency control of photomagnetic relaxation in a manganese(II) photoswitch 锰（II）光开关光磁弛豫的共价控制。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-29 DOI: 10.1038/s41557-026-02193-8

Sandra Kronenberger, Robert Naumann, Christoph Förster, Jan Klett, Dieter Schollmeyer, Luca M. Carrella, Eva Rentschler, Katja Heinze

{"title":"Covalency control of photomagnetic relaxation in a manganese(II) photoswitch","authors":"Sandra Kronenberger, Robert Naumann, Christoph Förster, Jan Klett, Dieter Schollmeyer, Luca M. Carrella, Eva Rentschler, Katja Heinze","doi":"10.1038/s41557-026-02193-8","DOIUrl":"10.1038/s41557-026-02193-8","url":null,"abstract":"Switching the electronic spin state in molecules by light is achieved via chemical bond reshuffling or light-induced excited spin state trapping. These procedures either require large-amplitude nuclear motions or cryogenic temperatures limiting their application in data storage or quantum computing devices. Here we show that a carbene manganese(II) complex undergoes light-induced excited spin state trapping at 141 K in solution and 112.5 K in the solid state. Irradiation quantitatively switches from low- to high-spin in solution and in the solid. The lifetime of the metastable high-spin state extrapolated from experimental data amounts to over 1 million years at 77 K. Key to success for the very long lifetime is the high reorganization energy due to high metal–ligand bond covalency, and hence, a large barrier height and width for the spin relaxation, paving the way for photo-switchable magnetic materials operating at ambient temperature. Light-induced excited spin state trapping (LIESST) has largely been limited to iron complexes and typically requires cryogenic temperatures or large nuclear rearrangements, limiting practical photomagnetic switching. Now a carbene manganese(II) complex achieves LIESST at 141 K in solution, demonstrating that increased metal–ligand covalency and rigidity can stabilize long-lived high-spin states and extend photomagnetic switching towards more practical temperature regimes.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 10","pages":"1729-1736"},"PeriodicalIF":24.5,"publicationDate":"2026-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41557-026-02193-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148352583","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Serendipitous twist in a hemithioindigo molecular motor enables energy storage 半靛蓝分子马达的偶然扭曲使能量储存成为可能。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-29 DOI: 10.1038/s41557-026-02191-w

Emma V. Puttock, Jos C. M. Kistemaker

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Trefoil polymers from a knotted synthon 三叶草聚合物从一个结的合成器。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-29 DOI: 10.1038/s41557-026-02197-4

Chenchen Du, Zhi Chen, Changqing Xu, Zhanhu Sun, Zhi-Hui Zhang, Xian-Guang Liu, Binhua Chen, Chenxin Zhang, Zhikai Li, Yin Rao, Deao Xu, Ningjin Zhang, Qiaowei Li, Heng Wang, Hai Qian, Liang Dai, Xiaopeng Li, David A. Leigh, Liang Zhang

{"title":"Trefoil polymers from a knotted synthon","authors":"Chenchen Du, Zhi Chen, Changqing Xu, Zhanhu Sun, Zhi-Hui Zhang, Xian-Guang Liu, Binhua Chen, Chenxin Zhang, Zhikai Li, Yin Rao, Deao Xu, Ningjin Zhang, Qiaowei Li, Heng Wang, Hai Qian, Liang Dai, Xiaopeng Li, David A. Leigh, Liang Zhang","doi":"10.1038/s41557-026-02197-4","DOIUrl":"10.1038/s41557-026-02197-4","url":null,"abstract":"Precise control over the presence and position of knots in polymers remains a long-standing synthetic challenge, with theory indicating broad implications for properties and function. Here we report on a topological synthon approach—extension and macrocyclization of an overhand knot—that enables the high yielding synthesis of closed-loop trefoiled polymers with narrow polydispersity and tunable topological parameters. From the same set of building blocks we prepared linear, cyclic and trefoiled topoisomers of matched chemical composition, allowing topology–property relationships to be examined directly. Low-temperature ultrahigh-vacuum scanning tunnelling microscopy resolved three conformers of trefoiled polystyrene, with high-, medium- and low-symmetry forms whose populations depend on chain length, local flexibility and solvation. Coarse‑grained Langevin dynamics reproduce these distributions and indicate that bending energy and conformational entropy govern conformer stability. Metal binding localizes the knotted region, reminiscent of protein/DNA knot translocation. The synthon also affords trefoiled poly(ethylene glycol) and trefoiled polystyrene–poly(ethylene glycol) diblock copolymers, demonstrating the generality of the approach across polymer backbones. An overhead knot that serves as a topological synthon enables the high-yield synthesis of trefoiled polymers with precise control over knotting. Topology–property relationships are then investigated across different polymer backbones, and the knotting influence on these properties revealed.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 10","pages":"1708-1716"},"PeriodicalIF":24.5,"publicationDate":"2026-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41557-026-02197-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148349335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Long live the triplet germylene 二甲苯万岁。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-26 DOI: 10.1038/s41557-026-02179-6

Terrance J. Hadlington

引用次数: 0

Concise synthesis and strain-release diversification of bridgehead-substituted [2]-ladderanes 桥头堡取代bbb -阶梯烷的简捷合成及其释放多样性。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-26 DOI: 10.1038/s41557-026-02196-5

Zongbin Jia, Hugo A. Salazar, Jet Tsien, Yixuan Ma, Olivia L. Coyle, Eric Crossley, Ricardo Alvarado, Yuzuru Kanda, Noelle Williams, Shuming Chen, Tian Qin

{"title":"Concise synthesis and strain-release diversification of bridgehead-substituted [2]-ladderanes","authors":"Zongbin Jia, Hugo A. Salazar, Jet Tsien, Yixuan Ma, Olivia L. Coyle, Eric Crossley, Ricardo Alvarado, Yuzuru Kanda, Noelle Williams, Shuming Chen, Tian Qin","doi":"10.1038/s41557-026-02196-5","DOIUrl":"10.1038/s41557-026-02196-5","url":null,"abstract":"Strained hydrocarbons offer privileged platforms for accessing otherwise elusive reactivity and molecular architectures. Among these, [2]-ladderane scaffolds hold considerable promise, yet modular access to diversely functionalized derivatives remains a major challenge. Here we report a concise and scalable strategy for the efficient synthesis of bridgehead-substituted [2]-ladderanes from readily available precursors. The resulting ladderanes serve as versatile intermediates for programmable, regioselective bridgehead functionalization and strain-release cycloadditions with electron-deficient alkenes, granting access to a broad array of multisubstituted bicyclo[2.2.2]octanes (BCOs). Furthermore, BCO scaffolds were leveraged for site-selective diversification and as saturated isosteres for benzene rings in pharmaceutically relevant molecules, leading to enhanced three-dimensionality and tunable physicochemical properties. Collectively, this work overcomes long-standing synthetic limitations and establishes bridgehead-substituted [2]-ladderanes and BCOs as modular platforms for complex molecule construction and rational molecular design. Among strained hydrocarbons, [2]-ladderanes hold considerable promise, but their modular synthesis and downstream functionalization remain challenging. Now, a concise and scalable approach for the synthesis of bridgehead-substituted ladderanes has been developed. These compounds can then be further transformed into diverse bicyclo[2.2.2]octanes via strain-release cycloadditions.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 8","pages":"1404-1412"},"PeriodicalIF":24.5,"publicationDate":"2026-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336098","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Ketones to ketyls by radical relocation 酮通过自由基重新定位变成了酮。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-25 DOI: 10.1038/s41557-026-02181-y

Adam Noble

引用次数: 0

Molecular rotary motors switch direction 分子旋转马达切换方向。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-25 DOI: 10.1038/s41557-026-02189-4

Beatrice S. L. Collins

引用次数: 0

Molecular neighbours reshape protein dynamics 分子邻居重塑蛋白质动力学。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-25 DOI: 10.1038/s41557-026-02194-7

Lars V. Schäfer

引用次数: 0

Singlet fission mediates carotenoid-to-bacteriochlorophyll energy transfer in purple photosynthetic bacteria 紫色光合细菌单线态裂变介导类胡萝卜素到细菌叶绿素的能量转移。

IF 24.5 1区化学

Nature chemistry Pub Date : 2026-06-23 DOI: 10.1038/s41557-026-02186-7

Shuangqing Wang, George A. Sutherland, James P. Pidgeon, Mateja Šmitran, David J. K. Swainsbury, Elizabeth C. Martin, Cvetelin Vasilev, Andrew Hitchcock, Daniel J. Gillard, Ravi Kumar Venkatraman, Dimitri Chekulaev, Alexander I. Tartakovskii, C. Neil Hunter, Jenny Clark

{"title":"Singlet fission mediates carotenoid-to-bacteriochlorophyll energy transfer in purple photosynthetic bacteria","authors":"Shuangqing Wang, George A. Sutherland, James P. Pidgeon, Mateja Šmitran, David J. K. Swainsbury, Elizabeth C. Martin, Cvetelin Vasilev, Andrew Hitchcock, Daniel J. Gillard, Ravi Kumar Venkatraman, Dimitri Chekulaev, Alexander I. Tartakovskii, C. Neil Hunter, Jenny Clark","doi":"10.1038/s41557-026-02186-7","DOIUrl":"10.1038/s41557-026-02186-7","url":null,"abstract":"Photosynthesis, the foundation of most life, begins when sunlight is captured by (bacterio)chlorophyll ((B)Chl) and carotenoid (Crt) pigments. These molecules are arranged so that captured energy migrates rapidly to reaction centres, where it is stored as a charge separation. The complementary absorption of Crt and (B)Chl pigments, and rapid energy transfer between them, underpins solar harvesting. Here we report a Crt-to-BChl energy transfer mechanism mediated by singlet fission, in which a high-energy singlet exciton (with spin quantum number S = 0) is converted into two low-energy triplet (S = 1) excitons. In purple photosynthetic bacteria, the Crt S2 singlet exciton splits into Crt and BChl triplet excitons on adjacent sites. Once formed, the triplets transfer cooperatively to BChl and onwards to reaction centres. Energy is transferred from a singlet Crt state, via the spin-protected long-lived triplet pair, to a singlet BChl state. Thus, this singlet fission-mediated mechanism augments solar energy harvesting for photosynthesis. The biological role of singlet fission—where two excitons are generated by one photon—is poorly understood. Now it has been shown that heterofission occurs in bacterial light-harvesting complexes, creating a triplet-pair reservoir that enhances carotenoid-to-bacteriochlorophyll energy transfer efficiency and temporarily staggers energy delivery to the reaction centre.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 9","pages":"1611-1619"},"PeriodicalIF":24.5,"publicationDate":"2026-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41557-026-02186-7.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148304977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0