Nature synthesis最新文献_第9页

A crystalline dithorium complex with a Th–Th bond 带Th-Th键的结晶型钍配合物

IF 2

Nature synthesis Pub Date : 2025-04-11 DOI: 10.1038/s44160-025-00789-5

Weiming Sheng, Fei Xie, Thayalan Rajeshkumar, Yue Zhao, Yufei Jiang, Wang Chen, Shengfa Ye, Laurent Maron, Congqing Zhu

{"title":"A crystalline dithorium complex with a Th–Th bond","authors":"Weiming Sheng, Fei Xie, Thayalan Rajeshkumar, Yue Zhao, Yufei Jiang, Wang Chen, Shengfa Ye, Laurent Maron, Congqing Zhu","doi":"10.1038/s44160-025-00789-5","DOIUrl":"10.1038/s44160-025-00789-5","url":null,"abstract":"Theoretical studies predict that homoatomic metal–metal bonds of f-block actinide elements should be ubiquitous. Surprisingly, however, the isolation and characterization of compounds featuring an actinide–actinide bond has proven challenging and the field remains undeveloped. Here we report a well-defined thorium dimer featuring a Th–Th two-centre one-electron (2c-1e) σ bond and a 2c-1e π bond. This thorium dimer was synthesized by reducing a Th(IV) chloride complex with potassium metal in tetrahydrofuran. Magnetic measurements indicate that this thorium dimer features exceedingly strong antiferromagnetic coupling between the two formal Th(III) centres with a coupling constant J ≤ −1,200 cm−1 such that the Th–Th interaction has covalent bond character. Detailed computational investigations further support the existence of the Th–Th bond in this molecule. These results demonstrate that diactinide complexes with actinide–actinide bonds are accessible but require an appropriate ligand framework to stabilize low-valent actinide centres. The isolation of compounds featuring an actinide–actinide bond is challenging. Now a well-defined Th(III) dimer with a Th–Th two-centre one-electron (2c-1e) σ bond and a 2c-1e π bond is synthesized. Theoretical and magnetic studies show that the open-shell singlet ground state and the two formal Th(III) centres exhibit strong antiferromagnetic coupling.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 8","pages":"987-994"},"PeriodicalIF":20.0,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123623","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

Twisting the future of two-dimensional halide perovskites 扭转二维卤化物钙钛矿的未来

IF 2

Nature synthesis Pub Date : 2025-04-11 DOI: 10.1038/s44160-025-00783-x

Keqiang Chen, Guogang Li

引用次数: 0

Geometric distortion as an enabling tool for organic synthesis 几何畸变是有机合成的有利工具

IF 2

Nature synthesis Pub Date : 2025-04-09 DOI: 10.1038/s44160-025-00776-w

Luca McDermott, Zach G. Walters, Allison M. Clark, Neil K. Garg

{"title":"Geometric distortion as an enabling tool for organic synthesis","authors":"Luca McDermott, Zach G. Walters, Allison M. Clark, Neil K. Garg","doi":"10.1038/s44160-025-00776-w","DOIUrl":"10.1038/s44160-025-00776-w","url":null,"abstract":"π-bonds are typically associated with well-defined arrangements of atoms. However, when the arrangement of atoms associated with these bonds becomes geometrically distorted, heightened reactivity is seen, enabling a wide range of transformations that can proceed under mild reaction conditions. As a result, molecules bearing complex structures can be rapidly assembled from simple building blocks. Here we describe the strategic use of synthetic building blocks containing π-bonds that feature geometric distortion, with a focus on recent applications to organic synthesis. The specific building blocks discussed are arynes, cyclic allenes, cyclic 1,2,3-trienes and anti-Bredt olefins. Developments in transition metal-mediated chemistry that enable previously unknown transformations are discussed, as well as new strategies for complex molecule and natural product synthesis that take advantage of geometrically distorted intermediates. We hope this Review will inspire future advances in the strategic use of geometric distortion in chemical synthesis. Although π-bonds are typically associated with having well-defined arrangements of atoms, ring constraints can lead to geometric distortion, resulting in heightened reactivity. These effects can be leveraged to enable synthetic transformations. This Review features processes wherein geometric distortion is leveraged to provide rapid access to structurally complex products.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 4","pages":"421-431"},"PeriodicalIF":20.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123411","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

Self-regulated facet stability during solution growth of perovskite crystals 钙钛矿晶体溶液生长过程中的自调节面稳定性

IF 2

Nature synthesis Pub Date : 2025-04-07 DOI: 10.1038/s44160-025-00786-8

Zhifang Shi, He Liu, Haoyang Jiao, Mingze Li, Zhenyi Ni, Liang Zhao, Jinsong Huang

{"title":"Self-regulated facet stability during solution growth of perovskite crystals","authors":"Zhifang Shi, He Liu, Haoyang Jiao, Mingze Li, Zhenyi Ni, Liang Zhao, Jinsong Huang","doi":"10.1038/s44160-025-00786-8","DOIUrl":"10.1038/s44160-025-00786-8","url":null,"abstract":"Solution growth of metal halide perovskites has enabled the development of applications including solar cells, light-emitting diodes and detectors, but the crystal growth mechanism remains unclear. Herein we studied the in situ transition of solute to crystals at the solid–liquid interface of methylammonium lead triiodide single crystals in γ-butyrolactone solution using microscopic spectroscopy. By establishing a temperature–bandgap relationship of the precursor solution, we observe a cooler interfacial region (1.5–4 μm from the crystal edge), explained by endothermic particle dissolution. This cooler region serves as a protective layer, hindering the attachment of particles with random orientations, maintaining the crystal facet orientation. The cooler interfacial protective layer is formed by the dissolution of particles driven by latent heat from crystallization and the concentration gradient of monomers at the interface. Disruption of the protective layer results in polycrystals with irregular facets. The understanding of the growth mechanisms of perovskite crystals provides insights for further improving the quality of solution-grown crystals. The in situ growth of methylammonium lead triiodide crystals in γ-butyrolactone is investigated. A cooler interfacial layer that serves as a protective layer to preserve the crystal facet orientation is observed.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 9","pages":"1088-1094"},"PeriodicalIF":20.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123648","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

Integrating a multitask graph neural network with DFT calculations for site-selectivity prediction of arenes and mechanistic knowledge generation 将多任务图神经网络与DFT计算相结合，用于芳烃选择性预测和机理知识生成

IF 2

Nature synthesis Pub Date : 2025-04-07 DOI: 10.1038/s44160-025-00770-2

Xinran Chen, Zi-Jing Zhang, Xin Hong, Lutz Ackermann

{"title":"Integrating a multitask graph neural network with DFT calculations for site-selectivity prediction of arenes and mechanistic knowledge generation","authors":"Xinran Chen, Zi-Jing Zhang, Xin Hong, Lutz Ackermann","doi":"10.1038/s44160-025-00770-2","DOIUrl":"10.1038/s44160-025-00770-2","url":null,"abstract":"The accurate prediction of reaction performance based on empirical knowledge paves the way to efficient molecule design. Compared with the human-summarized reaction knowledge of a focal dataset, the machine-learned quantitative structure–performance relationship of larger-scale datasets is more effective at accessing the entire chemical space. Here we report a multitask learning workflow combined with a mechanism-informed graph neural network to predict site selectivity for ruthenium-catalysed C–H functionalization of arenes. The multitask architecture enables the acquisition of related knowledge from the simultaneous learning tasks. The embedded reaction graph bridges the gap between previous mechanistic studies and reaction representation. Along with this mechanistic embedding, the developed multitask model demonstrates excellent interpolative and extrapolative ability on the reported dataset composed of 256 reactions, achieving an average site-selectivity prediction accuracy of 0.934 with a standard deviation of 0.007. The prediction scope ranges from simple to fused arenes and was even extended to heterocyclic indole derivatives in the additional out of sample tests containing 14 unseen instances. Furthermore, interpretation of the model promotes the development of a para-selective mechanistic model verified by density functional theory calculations. A multitask graph neural network is developed with mechanism-informed reaction graphs for site-selectivity prediction of ruthenium-catalysed C‒H functionalization of arenes. The extrapolative prediction ability of the model is verified by experimental tests. Interpretation of the model deepens our understanding of the origins of the site selectivity.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 7","pages":"877-887"},"PeriodicalIF":20.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s44160-025-00770-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123614","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

Regulation of Pd single-atom coordination for enhanced photocatalytic oxidation of toluene to benzaldehyde Pd单原子配位对甲苯光催化氧化制苯甲醛的调控作用

IF 2

Nature synthesis Pub Date : 2025-04-03 DOI: 10.1038/s44160-025-00782-y

Ruiyi Sun, Xing Cao, Junguo Ma, Hsiao-Chien Chen, Chen Chen, Qing Peng, Yadong Li

{"title":"Regulation of Pd single-atom coordination for enhanced photocatalytic oxidation of toluene to benzaldehyde","authors":"Ruiyi Sun, Xing Cao, Junguo Ma, Hsiao-Chien Chen, Chen Chen, Qing Peng, Yadong Li","doi":"10.1038/s44160-025-00782-y","DOIUrl":"10.1038/s44160-025-00782-y","url":null,"abstract":"Photocatalytic oxidation represents an effective means of hydrocarbon valorization, but achieving high-selectivity intermediate products at high substrate conversion remains challenging. Here single-atom Pd–O catalytic sites with different coordination environments are synthesized. The Pd–O3 coordinated single sites show the best catalytic performance for selective toluene oxidation, exhibiting a high benzaldehyde selectivity of 95% at 95% toluene conversion, and a benzaldehyde yield rate up to 12,000 μmol g−1 h−1, surpassing previously reported results. The Pd–O3 catalytic sites serve as the location of photogenerated charge separation and C(sp3)–H bond activation. These sites can trap the photogenerated holes effectively to enhance the charge-separation efficiency, improving the yield rate by a factor of 2.9 relative to the Bi2WO6 support. Additionally, the coordination structure weakens benzaldehyde adsorption, reducing overoxidation and improving reaction selectivity. This work highlights the importance of single-atom site coordination in optimizing the activity and selectivity of photocatalytic oxidation reactions. The design of active sites in single-atom photocatalysts has a large impact on the catalytic reactivity. Here single-atom Pd–O catalytic sites are engineered by regulating their coordination environments. The Pd–O3 sites exhibit enhanced activity and selectivity for photocatalytic oxidation of toluene to benzaldehyde.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 8","pages":"965-975"},"PeriodicalIF":20.0,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123624","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

An organophotoreductant for Z-alkene synthesis 一种用于z -烯烃合成的有机光还原剂

IF 2

Nature synthesis Pub Date : 2025-04-02 DOI: 10.1038/s44160-025-00796-6

Thomas West

引用次数: 0

Unusually stacked hexagonal boron nitride 异常堆积的六方氮化硼

IF 2

Nature synthesis Pub Date : 2025-04-01 DOI: 10.1038/s44160-025-00795-7

Alexandra R. Groves

引用次数: 0

Intermolecular 1,2,4-thiadiazole synthesis 分子间1,2,4-噻二唑合成

IF 2

Nature synthesis Pub Date : 2025-03-31 DOI: 10.1038/s44160-025-00794-8

Peter W. Seavill

引用次数: 0

Synthesis of a 2D tungsten MXene for electrocatalysis 电催化用二维钨MXene的合成

IF 2

Nature synthesis Pub Date : 2025-03-28 DOI: 10.1038/s44160-025-00773-z

Anupma Thakur, Wyatt J. Highland, Brian C. Wyatt, Jiayi Xu, Nithin Chandran B. S, Bowen Zhang, Zachary D. Hood, Shiba P. Adhikari, Emad Oveisi, Barbara Pacakova, Fernando Vega, Jeffrey Simon, Colton Fruhling, Benjamin Reigle, Mohammad Asadi, Pawel P. Michałowski, Vladimir M. Shalaev, Alexandra Boltasseva, Thomas E. Beechem, Cong Liu, Babak Anasori

{"title":"Synthesis of a 2D tungsten MXene for electrocatalysis","authors":"Anupma Thakur, Wyatt J. Highland, Brian C. Wyatt, Jiayi Xu, Nithin Chandran B. S, Bowen Zhang, Zachary D. Hood, Shiba P. Adhikari, Emad Oveisi, Barbara Pacakova, Fernando Vega, Jeffrey Simon, Colton Fruhling, Benjamin Reigle, Mohammad Asadi, Pawel P. Michałowski, Vladimir M. Shalaev, Alexandra Boltasseva, Thomas E. Beechem, Cong Liu, Babak Anasori","doi":"10.1038/s44160-025-00773-z","DOIUrl":"10.1038/s44160-025-00773-z","url":null,"abstract":"Two-dimensional (2D) transition metal carbides, nitrides and carbonitrides, known as MXenes, are of interest as electrocatalysts. Tungsten-based MXenes are predicted to have low overpotentials in the hydrogen evolution reaction but their synthesis has proven difficult due to the calculated instability of their hypothetical MAX precursors. In this study, we present a theory-guided synthesis of a tungsten-based MXene, W2TiC2Tx, derived from a non-MAX nanolaminated ternary carbide (W,Ti)4C4−y precursor by the selective etching of one of the covalently bonded tungsten layers. Our results indicate the importance of tungsten and titanium ordering, the presence of vacancy defects in the metal layers, and the lack of oxygen impurities in the carbon layers for the successful selective etching of the precursor. We confirm the atomistic out-of-plane ordering of tungsten and titanium using computational and experimental characterizations. The tungsten-rich basal plane endows W2TiC2Tx MXene with a high electrocatalytic hydrogen evolution reaction performance (∼144 mV overpotential at 10 mA cm−2). This study reports a tungsten-based MXene synthesized from a covalently bonded non-MAX precursor, adding to the synthetic strategies for 2D materials. The theory-guided synthesis of a tungsten-based W2TiC2Tx MXene from a non-MAX nanolaminated ternary carbide (W,Ti)4C4−y is reported. The tungsten-rich basal plane of the W2TiC2Tx MXene is then examined for the electrocatalytic hydrogen evolution reaction using a combined experimental and theoretical approach.","PeriodicalId":74251,"journal":{"name":"Nature synthesis","volume":"4 7","pages":"888-900"},"PeriodicalIF":20.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123087","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