Nature chemistry最新文献

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 21.8 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":"https://doi.org/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.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"31 1","pages":""},"PeriodicalIF":21.8,"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 21.8 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":"https://doi.org/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.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"37 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","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 21.8 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 21.8 1区化学

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

引用次数: 0

Catalytic C(sp2) homologation of alkylboranes 烷基硼烷催化C（sp2）同源化

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-07-24 DOI: 10.1038/s41557-025-01854-4

Bradley W. Gardner, Gojko Lalic

引用次数: 0

Introducing metal–sulfur active sites in metal–organic frameworks via post-synthetic modification for hydrogenation catalysis 通过合成后改性在金属有机骨架中引入金属硫活性位点用于加氢催化

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-07-24 DOI: 10.1038/s41557-025-01876-y

Haomiao Xie, Milad Ahmadi Khoshooei, Mukunda Mandal, Simon M. Vornholt, Jan Hofmann, Luke M. Tufaro, Kent O. Kirlikovali, Dawson A. Grimes, Seryeong Lee, Shengyi Su, Susanne Reischauer, Debabrata Sengupta, Kira Fahy, Kaikai Ma, Xiaoliang Wang, Fanrui Sha, Wei Gong, Yongwei Che, Jenny G. Vitillo, John S. Anderson, Justin M. Notestein, Karena W. Chapman, Laura Gagliardi, Omar K. Farha

{"title":"Introducing metal–sulfur active sites in metal–organic frameworks via post-synthetic modification for hydrogenation catalysis","authors":"Haomiao Xie, Milad Ahmadi Khoshooei, Mukunda Mandal, Simon M. Vornholt, Jan Hofmann, Luke M. Tufaro, Kent O. Kirlikovali, Dawson A. Grimes, Seryeong Lee, Shengyi Su, Susanne Reischauer, Debabrata Sengupta, Kira Fahy, Kaikai Ma, Xiaoliang Wang, Fanrui Sha, Wei Gong, Yongwei Che, Jenny G. Vitillo, John S. Anderson, Justin M. Notestein, Karena W. Chapman, Laura Gagliardi, Omar K. Farha","doi":"10.1038/s41557-025-01876-y","DOIUrl":"https://doi.org/10.1038/s41557-025-01876-y","url":null,"abstract":"Metal–sulfur active sites play a central role in catalytic processes such as hydrogenation and dehydrogenation, yet the majority of active sites in these compounds reside on the surfaces and edges of catalyst particles, limiting overall efficiency. Here we present a strategy to embed metal–sulfur active sites into metal–organic frameworks (MOFs) by converting bridging or terminal chloride ligands into hydroxide and subsequently into sulfide groups through post-synthetic modification. We apply this method to two representative MOF families: one featuring one-dimensional metal–chloride chains and another containing discrete multinuclear metal clusters. Crystallographic and spectroscopic analyses confirm structural integrity and sulfide incorporation, and the transformation is monitored by in situ total scattering methods. The sulfided MOFs display enhanced catalytic activity in the selective hydrogenation of nitroarenes using molecular hydrogen. Density functional theory calculations indicate that sulfur incorporation promotes homolytic metal–ligand bond cleavage and facilitates H2 activation. This work establishes an approach to construct MOFs featuring accessible metal–sulfide sites.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"23 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144693852","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

Disordered interfacial H2O promotes electrochemical C–C coupling 无序界面H2O促进电化学C-C耦合

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-07-23 DOI: 10.1038/s41557-025-01859-z

Hao Zhang, David Raciti, Anthony Shoji Hall

{"title":"Disordered interfacial H2O promotes electrochemical C–C coupling","authors":"Hao Zhang, David Raciti, Anthony Shoji Hall","doi":"10.1038/s41557-025-01859-z","DOIUrl":"https://doi.org/10.1038/s41557-025-01859-z","url":null,"abstract":"There is growing interest in the conversion of CO2 and CO into energy-dense multi-carbon products to help mitigate climate change, but guiding selectivity remains challenging due to competing pathways. Here we show that tuning the structure of interfacial water using highly concentrated NaClO4 electrolytes enhances CO electroreduction to C2H4. Increasing the NaClO4 concentration from 0.01 to 10 molal increased the CO reduction rate 18-fold, achieving a Faradaic efficiency of 91% for multi-carbon products at −1.43 V versus the normal hydrogen electrode. Temperature-dependent CO reduction, combined with surface-enhanced Raman spectroscopy, revealed that changes in the interfacial H2O structure correspond to variations in the apparent activation enthalpy and entropy for the reduction of CO to C2H4. At higher ionic strength, increases in activation entropy were linked to disrupted hydrogen bonding and the emergence of non-hydrogen-bonded water modes, suggesting that disordered interfacial H2O layers facilitate CO reduction to C2H4. These findings offer valuable insights into how manipulating the structure of interfacial water can enhance the reduction of CO to multi-carbon products.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"4 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684946","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

Transition state tuning with concentrated electrolytes 用浓电解质调整过渡态

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-07-23 DOI: 10.1038/s41557-025-01882-0

Sebastian Z. Oener

引用次数: 0

Expedient access to methylamine with potential 有潜力的甲胺的权宜之计

IF 21.8 1区化学

Nature chemistry Pub Date : 2025-07-22 DOI: 10.1038/s41557-025-01877-x

Tristan von Münchow, Lutz Ackermann

引用次数: 0