Nature chemistry最新文献_第10页

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-08-04 DOI: 10.1038/s41557-025-01888-8

Panpan Ma, Zhangkai Cui, Hongjian Lu

{"title":"Deaminative Giese-type reaction","authors":"Panpan Ma, Zhangkai Cui, Hongjian Lu","doi":"10.1038/s41557-025-01888-8","DOIUrl":"10.1038/s41557-025-01888-8","url":null,"abstract":"Primary aliphatic amines are essential components in numerous functional molecules and rank among the most readily available commercial building blocks. Although commonly utilized as nitrogen nucleophiles, their application as alkyl sources for constructing (sp3)C–C(sp3) bonds remains a notable challenge. Here we present an approach integrating nitrogen-atom deletion into the aza-Michael reaction, thereby redirecting the classical pathway from (sp3)C–N bond formation to (sp3)C–C(sp3) bond construction. Leveraging commercially available O-diphenylphosphinylhydroxylamine as an efficient nitrogen-deletion reagent, this method enables a wide variety of primary aliphatic amines to serve as alkyl sources in couplings with structurally diverse electron-deficient olefins. This Giese-type reaction proceeds under mild conditions, achieves completion within 10 min and exhibits broad functional-group compatibility. By bridging two foundational transformations—the aza-Michael reaction and the Giese-type reaction—this approach interlinks their product spaces through a unified precursor library, substantially enhancing synthetic utility. Primary aliphatic amines are abundant building blocks but underutilized as alkyl sources in C–C bond formation. Now it has been shown that integrating nitrogen-atom deletion into the aza-Michael reaction redirects the classical pathway from (sp3)C–N bond formation to Giese-type (sp3)C–C(sp3) bond construction.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 10","pages":"1556-1564"},"PeriodicalIF":20.2,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144770015","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

Naphthalene diimides for G4s G4s用萘二亚胺

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-08-01 DOI: 10.1038/s41557-025-01870-4

Nina M. Allen, Guilherme A. Marczak Giorio, M. Carmen Galan

引用次数: 0

The enlightening history of sodium carbonate 碳酸钠的启蒙历史

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-08-01 DOI: 10.1038/s41557-025-01893-x

Bruce C. Gibb

引用次数: 0

The making of virtuous chemists 造就有道德的化学家

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-08-01 DOI: 10.1038/s41557-025-01883-z

Dominic T. Chaloner, Michelle Francl, T. Ryan Byerly

引用次数: 0

Stabilizing a Ce≡C triple bond through fullerene confinement 通过富勒烯约束稳定Ce≡C三键

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-08-01 DOI: 10.1038/s41557-025-01919-4

引用次数: 0

Isolation of halogen-substituted silylium ions 卤素取代硅离子的分离

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-07-31 DOI: 10.1038/s41557-025-01880-2

Tobias Randt, Morten Lehmann, Elisabeth Irran, Martin Kaupp, Hendrik F. T. Klare, Martin Oestreich

{"title":"Isolation of halogen-substituted silylium ions","authors":"Tobias Randt, Morten Lehmann, Elisabeth Irran, Martin Kaupp, Hendrik F. T. Klare, Martin Oestreich","doi":"10.1038/s41557-025-01880-2","DOIUrl":"https://doi.org/10.1038/s41557-025-01880-2","url":null,"abstract":"The existence and intermediacy of halogen-substituted silylium ions have been the subject of speculation for decades. These elusive reactive intermediates are synthetically attractive because of their computationally predicted super Lewis acidity and their relevance in several synthetic transformations such as recycling of waste from the Müller–Rochow process and hydrodefluorination of per- and polyfluoroalkyl substances. Here we report the generation and characterization of all halogen-substituted silylium ions of type [Alk2XSi(HCB11H5Br6)] (X = F, Cl, Br or I; Alk = Me, Et, iPr or tBu). While the established Corey hydride transfer reaction fails to make such ions in the condensed phase, the protolysis of the halosilanes Alk2XSi‒LG (LG = H or Ph) using Reed’s superacidic benzenium ion [H(C6H6)]+[HCB11H5Br6]− provides practical access. The full series of counteranion-stabilized iPr2XSi+ cations is isolated and crystallographically characterized. The obtained halogen-substituted silylium ions are more Lewis acidic than their known trialkyl- and hydrogen-substituted congeners, as verified by quantitative assessment of their fluoride ion affinities using density functional theory calculations.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"111 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144747662","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

Flame synthesis achieves compositionally tailorable high-entropy metal-containing nanomaterials 火焰合成实现了成分可定制的高熵含金属纳米材料

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-07-30 DOI: 10.1038/s41557-025-01894-w

Zhen Liu, Eirini Goudeli, Rui Guo, Houting Xie, Qinjian Luo, Laichun Zhao, Wanjun Xu, Joseph J. Richardson, Weijian Xu, Frank Caruso, Shuaijun Pan

{"title":"Flame synthesis achieves compositionally tailorable high-entropy metal-containing nanomaterials","authors":"Zhen Liu, Eirini Goudeli, Rui Guo, Houting Xie, Qinjian Luo, Laichun Zhao, Wanjun Xu, Joseph J. Richardson, Weijian Xu, Frank Caruso, Shuaijun Pan","doi":"10.1038/s41557-025-01894-w","DOIUrl":"10.1038/s41557-025-01894-w","url":null,"abstract":"High-entropy metal-containing nanomaterials have garnered interest in diverse fields such as electrocatalysis and energy conversion. Their synthesis typically requires high temperatures (>1,000 K) to facilitate homogeneous mixing and rapid transformation of metal precursors. However, current state-of-the-art approaches typically involve complex reaction environments and require specialized equipment and operations. Herein we demonstrate a versatile flame synthesis process to fabricate high-entropy metallic single atoms and/or nanoparticles supported on soot-like carbon via blending organometallic precursors into fuel (namely, paraffin wax) and subsequent burning. The high flame temperature (~1,800 K) enables strong metal–carbon association with tailorable chemistry and homogeneous bonding between dissimilar metallic elements (up to 25 metals studied), regardless of their thermodynamic compatibility. Additionally, we show high-performance electrosynthesis of hydrogen peroxide to highlight this approach as a promising method for electrocatalyst development. High-entropy nanomaterials, which incorporate multiple homogeneously dispersed elements, are promising for energy conversion, but typically require complex, high-temperature synthesis. Now a scalable flame synthesis method has been shown to produce tunable, high-entropy nanomaterials under facile conditions, enabling the design of advanced electrocatalysts for hydrogen peroxide production and other relevant applications.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 10","pages":"1497-1504"},"PeriodicalIF":20.2,"publicationDate":"2025-07-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737051","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

Bright triplet and bright charge-separated singlet excitons in organic diradicals enable optical read-out and writing of spin states 有机双自由基中明亮的三重态和明亮的电荷分离单线态激子使自旋态的光学读出和写入成为可能

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-07-29 DOI: 10.1038/s41557-025-01875-z

Rituparno Chowdhury, Petri Murto, Naitik A. Panjwani, Yan Sun, Pratyush Ghosh, Yorrick Boeije, Chiara Delpiano Cordeiro, Vadim Derkach, Seung-Je Woo, Oliver Millington, Daniel G. Congrave, Yao Fu, Tarig B. E. Mustafa, Miguel Monteverde, Jesús Cerdá, Giacomo Londi, Jan Behrends, Akshay Rao, David Beljonne, Alexei Chepelianskii, Hugo Bronstein, Richard H. Friend

{"title":"Bright triplet and bright charge-separated singlet excitons in organic diradicals enable optical read-out and writing of spin states","authors":"Rituparno Chowdhury, Petri Murto, Naitik A. Panjwani, Yan Sun, Pratyush Ghosh, Yorrick Boeije, Chiara Delpiano Cordeiro, Vadim Derkach, Seung-Je Woo, Oliver Millington, Daniel G. Congrave, Yao Fu, Tarig B. E. Mustafa, Miguel Monteverde, Jesús Cerdá, Giacomo Londi, Jan Behrends, Akshay Rao, David Beljonne, Alexei Chepelianskii, Hugo Bronstein, Richard H. Friend","doi":"10.1038/s41557-025-01875-z","DOIUrl":"10.1038/s41557-025-01875-z","url":null,"abstract":"Optical control of electron spin states is important for quantum sensing and computing applications, as developed with the diamond nitrogen vacancy centre. This requires electronic excitations, excitons, with net spin. Here we report a molecular diradical where two trityl radical groups are coupled via a meta-linked fluorene bridge. The singlet exciton is at lower energy than the triplet because electron transfer from one of the radical non-bonding orbitals to the other is spin allowed, set by the charging energy for the double occupancy of the non-bonding level, the Hubbard U. Both excitons give efficient photoluminescence at 640 and 700 nm with near unity efficiency. The ground state exchange energy is low, 60 µeV, allowing control of ground state spin populations. We demonstrate spin-selective intersystem crossing and show coherent microwave control. We report up to 8% photoluminescence contrast at microwave resonance. This tuning of the singlet Mott–Hubbard exciton against the ‘bandgap’ exciton provides a new design platform for spin–optical materials. Controlling electron spin states with light is vital for quantum technologies but requires electronic excitations with net spin. Now a molecular diradical with two trityl radical groups coupled via a meta-linked fluorene bridge has been developed that features luminescent singlet and triplet excitons. The spins in the ground state can be written and read using photons, giving rise to broad magnetic and microwave modulation of the photoluminescence.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 9","pages":"1410-1417"},"PeriodicalIF":20.2,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41557-025-01875-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719711","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

A bismuth-based analogue of the π-allyl cation 烯丙基阳离子的铋基类似物

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-07-29 DOI: 10.1038/s41557-025-01881-1

Sandeep Kumar, Kanishk Tomer, Priyabrata Ghana

引用次数: 0

An enzyme for high-yield, ATP-driven C-terminal thioester generation 一种用于高产、atp驱动的c端硫酯生成的酶

IF 20.2 1区化学

Nature chemistry Pub Date : 2025-07-25 DOI: 10.1038/s41557-025-01872-2

引用次数: 0