Chemical Science最新文献

{"title":"A simple synthesis of group 2 anthracenides and their use as reducing agents for polypnictogen ligand complexes","authors":"Lukas Adlbert, Martin Weber, Christoph Riesinger, Michael Seidl, Manfred Scheer","doi":"10.1039/d5sc04242a","DOIUrl":"https://doi.org/10.1039/d5sc04242a","url":null,"abstract":"By using an improved synthetic pathway, the anthracenides of the group 2 metals Ca, Sr, and Ba are straightforwardly accessible for subsequent organometallic syntheses. These highly reactive compounds are slightly soluble in tetrahydrofuran and can be used as synthons for group 2 metal transfer due to the lability of the anthracene substituent. These features were used to explore their reactivity towards the polyphosphorus ligand complexes [Cp*Fe(η<small>⁵</small>-P<small>₅</small>)] (Cp*C<small>₅</small>(CH<small>₃</small>)<small>₅</small>) and [Cp*Fe(η<small>^3:1</small>-(1-CH<small>₃</small>-2-PPh<small>₂</small>-P<small>₅</small>))], respectively. The resulting products, [Cp*Fe(µ-η<small>^4:2:1</small>-P<small>₅</small>)Mg(thf)<small>₃</small>]∙0.5thf (thf=tetrahydrofuran) and [{Cp*Fe(µ-η<small>^2:2:1</small>-(1-CH<small>₃</small>-2-PPh<small>₂</small>-P<small>₅</small>))}<small>₂</small>Mg(thf)<small>₂</small>]∙3thf, are first examples of molecular magnesium-containing polypnictogenide transition metal complexes without stabilization by N-donor ligands that are soluble in organic N-donor-free solvents. The P<small>₁₂</small> ligand in the latter complex is the first example of a 2,2’-diphosphanyl-substituted decaphosphadihydrofulvalen-shaped structural motif (2,2’-bis(diphenylphosphanyl)-1,1’-dimethyl-3,3’-bipentaphosphole). The complexes [Cp*Fe(µ<small>₃</small>-η<small>^4:4:1</small>-P<small>₅</small>)Sr(thf)<small>₄</small>]<small>₂</small>∙thf and [Cp*Fe(µ<small>₃</small>-η<small>^2:1:1:1:1</small>-(1-CH<small>₃</small>-2-PPh<small>₂</small>-P<small>₅</small>))Sr(thf)<small>₃</small>]<small>₂</small>∙2thf represent the first examples of a molecular polypnictogen compound of strontium that are stable in organic solvents","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"53 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144694164","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}

{"title":"Direct determination of multiphoton absorption cross-sections by transient absorption spectroscopy","authors":"Huajun He, Jia Wei Melvin Lim, Minjun Feng, Zengshan Xing, Tze Chien Sum","doi":"10.1039/d5sc03392f","DOIUrl":"https://doi.org/10.1039/d5sc03392f","url":null,"abstract":"Single- and multi-photon absorption cross-sections quantify the likelihood that a material will absorb one or more photons at a given wavelength. This critical parameter is fundamental to understanding light-matter interactions that underpin key applications in spectroscopy, photochemistry and advanced imaging techniques like multi-photon microscopy and deep tissue imaging. Conventional methods for measuring absorption cross-sections are often limited by sensitivity to sample morphology, type, concentration, and high excitation intensities – factors that can compromise reliability, increase experimental complexity, and risk sample damage. Herein, we present a direct, robust, and versatile method for quantifying absorption cross-sections across single- to multi-photon regimes, based on the saturation behaviour of transient absorption signals. Using this approach, we report for the first time the three-photon and four-photon absorption cross-sections of CsPbI<small>₃</small> perovskite nanocrystals and CdSe/ZnS quantum dots under 1700 nm and 2100 nm excitation. These values exceed those of incumbent materials used for mouse deep-brain imaging by at least an order of magnitude. Our method does not rely on photoluminescence signals, making it suitable for weakly or non-emissive materials. Importantly, our work provides a powerful generalizable tool to accelerate the discovery and optimization of next generation photon-harvesting materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144694162","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}

{"title":"Special Solvating Effects of Mixed Water and Alcohols Revealed by Molecular Aggregations","authors":"Linghao Meng, Rong Wei, Zhaoxin Xie, Di Zhang, Xiaohan Wan, Han Han, Wenjing Shi, Ziqi Zhu, Xiao Xiao, Yi Qin Gao, Dahui Zhao","doi":"10.1039/d5sc03588k","DOIUrl":"https://doi.org/10.1039/d5sc03588k","url":null,"abstract":"Owing to the green nature, good miscibility and tunable polarity, alcohols are widely used as popular co-solvents of water in the supramolecular assembling. Intriguingly, the solvating properties of water/alcohol mixtures often show a complex dependence on the composition. Herein, the unusual solvating effects of water and alcohol mixtures are elucidated by examining the aggregation motif changes of amphiphilic polycycles bearing more polar side chains. While the molecule assembles into long fibrous J-aggregates in pure water and alcohols, H-aggregates of smaller sizes appear in water-alcohol mixtures. Similar dissociation is found to occur to different low-carbon water-alcohol systems, but the H/J switching takes place at different volume ratios, depending on the alcohol structure. It is thus speculated that the aggregate dissociations reflect an enhanced solubilizing ability of the mixed solvents, which is assumed to be related to the microscopic structures of the water-alcohol binary systems. That is, the highly structured networks formed by mixed water and alcohols possess enhanced solvating capacity for the amphiphilic molecules, and alcohols having longer alkyl groups and thus forming larger structured hydration shells in water disrupt the aggregation more effectively. Molecular dynamic simulations have provided supportive evidence for the special solubilizing properties of mixed water and alcohols.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684980","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}

{"title":"Merging Carboxylic Acids with Metal-Catalyzed Hydrogen Atom Transfer (MHAT) Chemistry via Alkene-Functionalized Redox-Active Esters","authors":"Laura G. Rodríguez, Aina Serra, Josep Bonjoch, Ben Bradshaw","doi":"10.1039/d5sc04274g","DOIUrl":"https://doi.org/10.1039/d5sc04274g","url":null,"abstract":"The development of general methods for radical bond formation remains a central goal in organic synthesis, particularly those that enable diverse transformations from simple, abundant starting materials. Here, we report a unified approach that merges carboxylic acid activation with metal-catalyzed hydrogen atom transfer (MHAT) to enable the generation and selective functionalization of open-shell intermediates under a single catalytic system. Key to this strategy is the design of a redox-active ester bearing an internal alkene “trigger” that undergoes regioselective MHAT using Fe(acac)₃ and phenylsilane, leading to decarboxylative radical formation under mild conditions. This platform supports the synthesis of a wide array of products via C–C, C–heteroatom, and C–H bond-forming processes, accessed solely by varying the radical acceptor. Notably, it enables the formation of linear coupling products—previously inaccessible under conventional MHAT conditions—via access to primary radical intermediates. We anticipate that this conceptually distinct mode of activation will find applications in modular synthesis, late-stage functionalization, and the generation of medicinally relevant analogs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"172 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684998","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}

{"title":"Understanding Polymer Encapsulation of Enzyme: A Dissipative Particle Dynamics Simulation Study on the Regulation of Structural Characteristics of Polymer Nanocapsule","authors":"Zhong-Yuan Lu, Huimin Gao, Bin Xu, Bin Li","doi":"10.1039/d5sc02655e","DOIUrl":"https://doi.org/10.1039/d5sc02655e","url":null,"abstract":"Enzymes play a crucial role as catalysts in biological processes, and enzyme therapy—utilizing biological enzymes—has gained significant attention for disease treatment. However, a critical challenge in enzyme therapy is the effective delivery of exogenous enzymes while maintaining their catalytic activity. Encapsulating enzymes in polymers offers a promising strategy to enhance their stability, prolong their half-life in the bloodstream, and improve biocompatibility. In this study, we employ dissipative particle dynamics (DPD) simulations combined with a reaction model to investigate the polymerization dynamics and the formation of a polymer nanocapsule around a nanoparticle that models an enzyme under mild reaction conditions. Our results show that the formation of a well-structured polymer nanocapsule depends on the strong attraction between monomers and the nanoparticle surface, low hydrophobicity, moderate polymerization rates, and weak chain stiffness. To optimize polymer nanocapsule preparation, we also examine the ratio of initiator to crosslinker at different monomer concentrations, identifying conditions that lead to a well-constructed polymer nanocapsule with high monomer participation. Our model is adaptable to various enzyme and monomer types by modifying their structures and properties, offering valuable insights for the future design of polymer nanocapsules in enzyme delivery.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"110 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684974","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}

{"title":"Water-mediated synthesis of hydrogen-bonded metal–organic frameworks","authors":"Zongjing Xiao, Pengfei Li, Beibei Sun, Xinrui Bao, Lei Gan, Huajun Yang","doi":"10.1039/d5sc02337h","DOIUrl":"https://doi.org/10.1039/d5sc02337h","url":null,"abstract":"The integration of different types of frameworks into one would provide a unique opportunity for the development of crystalline frameworks that can combine the unique advantages of each. In this work, we successfully realize the integration of metal–organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) through the synthesis of two hydrogen-bonded metal–organic frameworks, namely <strong>NNM-1(M)</strong> (M = Cu or Ni). The structures of <strong>NNM-1</strong> are built on (4, 4)-squared coordinative metal–organic layers. Between the layers, two adjacent protonated carboxylic groups serve as both hydrogen donors and acceptors, leading to the formation of hydrogen-bonded pillars with <em>R</em><small>₂</small><small>²</small>(8) dimeric hydrogen bonding, the most common hydrogen-bonded motif in HOFs. It was found that water plays a vital role in the structural transformation from 3D MOFs to H-MOFs here. Under a low pressure of 0.1 bar, the material <strong>NNM-1(Cu)</strong> can adsorb 4.84 mmol g<small>⁻¹</small> of NH<small>₃</small>, making it a promising adsorbent for ammonia capture.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684978","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}

{"title":"Zinc Substituted Carbenes: Synthesis, Structure, and Ambiphilic Reactivity","authors":"Shengjie Jiang, Ganping Wang, Yanping Cai, Laurent Maron, Xin Xu","doi":"10.1039/d5sc03342j","DOIUrl":"https://doi.org/10.1039/d5sc03342j","url":null,"abstract":"Metal-substituted carbenes are fundamentally important as they represent the limiting configurations of metal carbynes. However, structurally characterized examples are still rare, and their reactivity remains underexplored. Herein, we report the first synthesis, characterization, and reactivity studies of zinc-substituted carbenes. UV irradiation of zinc diazoalkyl complexes LZnC(N2)P [L = [(ArNCMe)2CH]−, P = (DippNCH2)2P, Ar = Dipp or Mes, Dipp = 2,6-iPr2C6H3, Mes = 2,4,6-Me3C6H2] generates Zn(II)-substituted carbenes LZnCP with concomitant N2 release. The Zn–C–P moiety features nearly linear carbene centers, deviating from conventional carbene geometry. Computational studies indicate a singlet ground state stabilized through synergistic effects of C–P π-interaction and carbene lone-pair delocalization towards the Zn center. Treatment of LZnCP with CO2 selectively affords zincated ketene via nucleophilic attack and tandem C=O double bond cleavage. It reacts with 4-dimethylaminopyridine to form a carbene-Lewis base adduct exhibiting electrophilic reactivity. Furthermore, zinc-substituted carbenes enable direct transition metals coordination to give the heterobimetallic Zn/M (M = Ag+, Au+, Ni) μ-carbyne complexes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"53 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684985","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}

{"title":"What Distinguishes the Strength and the Effect of a Lewis Base: Insights with a Strong Chromogenic Silicon Lewis Acid","authors":"Lennart Stoess, Lutz Greb","doi":"10.1039/d5sc03200h","DOIUrl":"https://doi.org/10.1039/d5sc03200h","url":null,"abstract":"Quantifying Lewis basicity (LB) is essential for understanding chemical reactivity. Yet, the relationship between the intrinsic thermodynamic strength of a Lewis base and the effect it induces at a bound Lewis acid remains poorly defined, especially across structurally diverse bases. Here, we introduce a chromogenic silicon-based Lewis acid to disentangle this relationship via optical spectroscopy and computational analysis. Extending our previously developed concept of global and effective Lewis acidity (gLA and eLA), we propose analogous descriptors for Lewis basicity: global Lewis basicity (gLB) and effective Lewis basicity (eLB). Our findings reveal that gLB and eLB are distinct and independently varying properties. However, unlike for Lewis acidity—where the offset of gLA and eLA is governed by deformation energy—the divergence of gLB and eLB is dominated by solvation of the Lewis base. Specifically, solvation energy significantly affects adduct formation thermodynamics (gLB) but has minimal influence on the induced optical response (eLB). Furthermore, the chromogenic probe enables identification of π-type Lewis basicity contributions. The distinction developed in this work refines the conceptual framework of Lewis pair interactions and highlights the importance of solvation and electronic structure when applying LB descriptors in different chemical contexts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"25 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144685027","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}

{"title":"Strategic molecular engineering of non-fused non-fullerene acceptors: efficiency advances and mechanistic insight","authors":"Minmin Chen, Yong Zhang, Jinglin Liu, Qungui Wang, Peng Song, Yuanzuo Li","doi":"10.1039/d5sc00528k","DOIUrl":"https://doi.org/10.1039/d5sc00528k","url":null,"abstract":"Non-fullerene acceptor materials characterized by fused ring structures have garnered considerable attention due to their tunable molecular architectures, extensive and robust absorption spectra, and high photoelectric conversion efficiencies. Nonetheless, these materials present challenges, such as complex synthetic processes, elevated costs, and significant fabrication difficulties, which markedly impede their commercial viability. In light of these challenges, exploration of non-fused ring acceptors that are easier to synthesize and exhibit superior device characteristics has been proposed as a promising solution. Thus, the investigation of these structural acceptor materials is of substantial significance. This study reviews recent advances in non-fused ring acceptors for organic solar cells, guided by various engineering modulation strategies. The effects of molecular design approaches, including non-covalent conformation-locking engineering, core engineering, side-chain engineering, and substituent engineering, on device performance are examined. Finally, the mechanisms governing the behavior of non-fused-ring acceptor materials across different strategies are outlined, and future development trends and applications are anticipated.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144694165","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}

{"title":"C−C Bond Cleavage and Carbonylation Enabled by an NNN-Pincer Uranium Scaffold via Metal-Arene Interaction","authors":"Yue Pang, Thayalan Rajeshkumar, Rosario Scopelliti, Laurent Maron, Marinella Mazzanti","doi":"10.1039/d5sc04248h","DOIUrl":"https://doi.org/10.1039/d5sc04248h","url":null,"abstract":"Metal-arene complexes have recently attracted an increasing interest in f-element chemistry, but the functionalization of arenes mediated by uranium-arene interactions is limited to a single example. Here, we report a new uranium-biphenylene complex supported by a bulky rigid trianionic NNN-pincer ligand in which the uranium-arene interaction is able to promote C−C bond cleavage and functionalization with CO under mild conditions to yield a U-bound 9-fluorenone. Reduction of the U(IV)-pincer complex [NNN-U(THF)Cl2K(THF)3]2 (1) with KC8, in the presence of biphenylene, results in the terminal arene complex [NNN-U(THF)(biphenylene)][K(THF)5] (3). DFT studies of 3 indicate the presence of two unpaired electrons located at the uranium center, in line with a U(IV) and a biphenylene dianion. Complex 3 undergoes Caryl−Caryl bond cleavage of the biphenylene ligand, affording [NNN-U(THF)(2,2'-biphenyl)][K(THF)2] (4). DFT studies indicated that, due to the interaction between the biphenylene dianion and the uranium, a concerted ring opening reaction can occur on the strained four members ring to yield 4 while the uranium center retains a +IV oxidation state. Complex 4 undergoes facile CO insertion into the U−Caryl bond, followed by the Caryl−Ccarbonyl bond formation, yielding [NNN-U(THF)2(fluorenone)][K(THF)4] (5). This work demonstrates the potentials of uranium-arene interactions to promote arene activation and functionalization","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"53 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684955","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}