Chemical Science最新文献

{"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}

{"title":"Tautomer aspects in the excited-state dynamics in 2-thiocytosine: intersystem crossing in the absence of the thiocarbonyl group","authors":"Bijay Duwal, Isabel Eder, Leticia González, Sebastian Mai, Susanne Ullrich","doi":"10.1039/d5sc01442e","DOIUrl":"https://doi.org/10.1039/d5sc01442e","url":null,"abstract":"Molecular tautomerism is ubiquitous in nature and plays a crucial role in regulating biological function. In nucleobases, for example, structural tautomerism not only influences base pairing and genetic coding in DNA but also modulates the molecular response to UV irradiation. The photostability of the nucleobases depends on efficient internal conversion and is highly sensitive to structural variations and micro-environmental effects. Among the pyrimidine bases, cytosine exhibits the greatest number of tautomeric forms, offering a rich landscape to explore diverse structural scenarios, while simultaneously posing significant experimental challenges. This study builds on that context by unveiling the gas-phase photophysics of 2-thiocytosine (2TC) from a unique tautomer perspective. Specifically, it elucidates the decay mechanism in the absence of a thiocarbonyl group but under the influence of chalcogen heavy atom substitution. In solution, 2TC exists in its thion form, whose photodynamics are characterized by efficient intersystem crossing to the triplet manifold. Electronic and structural factors associated with the thiocarbonyl group play a crucial role in suppressing internal conversion pathways to the ground state—pathways that are otherwise active in canonical cytosine. This ISC mechanism is tautomer specific and does not apply to the thiol form, which dominates in the gas phase. Time-resolved photoelectron spectroscopy of thiol-2TC reveals ultrafast internal conversion dynamics, alongside the emergence of a long-lived state with nanosecond lifetime. The latter distinguishes the photodynamics from its canonical counterpart, enol cytosine. <em>Ab initio</em> calculations provide detailed insights into the deactivation mechanism of thiol 2TC and clarify the differences on the effect of thionation on both tautomeric forms of cytosine. Finally, we discuss how protonation (and hydrogen bonding) can modulate intersystem crossing in thiobases, with broader implications to other thiocarbonyl-containing compounds.","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":"144684976","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":"Ultrathin potassiophilic carbon skin design achieving ultra-stable potassium metal anode","authors":"Zhibin Li, Zheng Hu, Miaoran Deng, Liang Ma, Jinliang Li, Wenjie Mai","doi":"10.1039/d5sc04233j","DOIUrl":"https://doi.org/10.1039/d5sc04233j","url":null,"abstract":"Due to the complex fabrication process and poor reversibility of potassium (K) metal, developing high-performance host materials for K metal anodes remains a significant challenge. In this work, an ultrathin and dense N-doped carbon layer was uniformly loaded onto carbon fibers (N-CF) as a host for K metal anodes. This design effectively regulates the intrinsic adsorption behavior of metallic K, mitigating the effects of local uneven electric fields in the electrolyte and enabling stable cycling performance under high current densities. We found that the N functional groups synergistically constructed a robust potassiophilic surface, facilitating spontaneous and rapid integration with molten K. This process effectively suppresses dendrite growth and ensures stable cycling of the K metal anode, even under ultra-high current densities. Thus, the symmetric cell with N-CF host exhibited remarkable cycling stability, maintaining stable cycling performance over 4300 h at 0.5 mA cm-2/0.5 mAh cm-2. Furthermore, the anode demonstrated low polarization voltage and exceptional stability even at 9 mA cm-2, underscoring its superior dendrite inhibition capability. Ultimately, the outstanding stability of the N-CF@K metal anode enabled impressive performance in full-cell testing with Prussian blue cathode. After 300 cycles, the full cell retained a high specific capacity of 91 mAh g-1 and a capacity retention of 91.8% at 500 mA g-1. We believe that our work offers a novel chance to design an advanced host for achieving stable K metal anode performance under ultra-high current densities.","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":"144684972","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":"Multi-enzyme reaction inspired photocatalysis for solar-driven CO2 reduction to ethane","authors":"Qian Zhang, Shuaiqi Gao, Xiao Zhao, Huiyong Wang, Yingying Guo, Zhimin Liu, Jianji Wang","doi":"10.1039/d5sc03323c","DOIUrl":"https://doi.org/10.1039/d5sc03323c","url":null,"abstract":"Photocatalytic CO<small>₂</small> reduction for the production of multicarbon products has emerged as a green and sustainable technology, which shows great potential and cost-effectiveness. However, photocatalytic synthesis of two-carbon (C<small>₂</small>) compounds is quite challenging due to the high activation barrier of the C–C coupling reaction and low content of intermediates. Herein, inspired by the tandem synthesis in multi-enzyme reactions, Cu–N<small>₄</small> and Mo–N<small>₄</small> active sites have been designed and integrated in CuPor-POP-Mo as cascade dual metal sites for efficient photocatalytic reduction of CO<small>₂</small> to ethane (C<small>₂</small>H<small>₆</small>) for the first time. Significantly, an excellent C<small>₂</small>H<small>₆</small> production rate of 472.5 μmol g<small>⁻¹</small> h<small>⁻¹</small> and a high product selectivity of 87.5% (electron selectivity ∼97.5%) have been achieved, which are the record high values in photocatalytic C<small>₂</small>H<small>₆</small> production by using porous polymer catalysts. <em>In situ</em> spectral characterization studies and DFT calculations indicate that the Cu site enhanced the localized surface coverage of *CO on CuPor-POP-Mo, while the Mo site of the photocatalyst triggered the C–C coupling of *CO intermediates, and the energy barrier of which was synergistically lowered by Cu and Mo sites, resulting in highly effective C<small>₂</small>H<small>₆</small> production. This work develops novel metal sites for ethane production and enables precise modulation of *CO intermediate coverage to decrease the energy barrier for *OCCO generation, thus opening a new pathway for highly selective photocatalytic CO<small>₂</small> reduction toward value-added chemicals and fuels.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"114 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684979","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":"Visible Light Activation of C-Cl and C-F Bonds in Persistent Organic Pollutants Using Cerium(III) Triamidoamine Complex","authors":"Adrien Combourieu, Stella Christodoulou, Laurent Maron, eachann assendjee, Nicolas Casaretto, Bich Tuyen Phung, Akos Banyasz, Olivier Maury, Matthew Gregson, Ashley Wooles, Stephen Liddle, Cédric Tard, Grégory Nocton, Grégory Danoun","doi":"10.1039/d5sc03626g","DOIUrl":"https://doi.org/10.1039/d5sc03626g","url":null,"abstract":"Procedures for activating and degrading compounds containing carbon-halogen bonds are highly sought after due to the environmental persistence and potential hazards of such compounds. Such activations are challenging because of the high stability of these bonds, particularly those with C-F bonds. Here, we report on the activation of carbon-halogen bonds, including C-F bonds, by the cerium(III)-triamidoamine complex CeIIITRENTIPS (1, TRENTIPS = tris-(2-(tri-iso-propylsilylamidoethyl)amine). Under light irradiation, 1 reaches a strongly negative excited state redox potential, and our measurements enable it to be estimated as − 3.2 V relative to Cp2Fe0/+. Hence, the photo-reactivity of 1 with carbon-halogen bonds has been established with numerous examples, including Persistent Organic Pollutants (POPs) and fluorinated compounds. The photoactivation of POPs is rapid, but the photoactive nature of the cerium(IV) products precludes complete conversion. This study provides insight into the activation of POPs that may benefit the future design of photodegradation approaches for these highly problematic compounds.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684981","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":"Divergent reactivity of intramolecular cycloadditions of keteniminium ions with alkynes: [4+2] or [2+2]?","authors":"Sangjun Lee, Thomas R. Hoye","doi":"10.1039/d5sc02212f","DOIUrl":"https://doi.org/10.1039/d5sc02212f","url":null,"abstract":"We describe here divergent reactivity in the intramolecular cyclizations of a family of keteniminium ions (KIs) that contain a tethered alkyne. The KI precursors were tertiary amides having (i) unsaturation (arene or alkene) located β,γ to the amide carbonyl and (ii) an alkyne tethered through the amide nitrogen atom. The KIs were generated by the action of triflic anhydride and a pyridine base at 0 °C. Substrates having a three-atom linker between the central carbon atom of the KI undergo unprecedented [4 + 2] cycloadditions between the alkyne and the styrenic/dienic subunit of the conjugated KI leading to indoline or carbazole derivatives. DFT computations suggest that the reaction proceeds by a stepwise mechanism. In contrast, substrates with a four- or five-atom tether undergo [2 + 2] cycloaddition to afford isolable, fused, cyclobutenyl iminium ions further useful as synthons.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"12 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684999","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":"Visible-Light Photoredox Catalysis of Polydopamine with Triethanolamine in Water","authors":"Hoyun Kim, Dokyeong Lee, Young Jae Jung, Sung Ho Yang, Hye Jin Lee, Hong-In Lee, Jungkyu K. Lee","doi":"10.1039/d5sc04938e","DOIUrl":"https://doi.org/10.1039/d5sc04938e","url":null,"abstract":"Polydopamine (PDA), a synthetic melanin, has recently emerged as a photoreactive material, contrasting with its conventional role in photoprotection. Especially, its photochemical reactivity under visible light offers new perspective on the role of melanin and opens up potential applications in biomedical engineering and energy conversion. However, the mechanism of the visible light-induced reactions is still not well understood, necessitating further systematic investigation. To address this challenge, we carefully investigated its photoredox catalysis under visible-light irradiation, focusing on electron transfer processes in the presence of triethanolamine as an electron donor. We explored various aspects, including its size-dependent reactivity, electrochemical and photophysical properties, and the characterization of generated radical species. Furthermore, we sought to optimize photoinitiated polymerization under various reaction conditions, such as different concentrations, monomers, and atmospheres. The use of water as a solvent is generally considered as safe and poses minimal risk to human health and safety compared to many organic solvents. These results are crucial for advancing the understanding of melanin’s photoredox catalytic mechanism and for developing innovative biocompatible photoreactive materials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"143 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677782","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":"A Pair of Strongly Reductive and Oxidative Photocatalysts for the General Upcycling of Biomass Derivatives and Plastic Wastes","authors":"Hao Cui, Xiang Chen, Xiong She, Wen-Xin Su, Shi-Chao Chen, Xiao Zhang","doi":"10.1039/d5sc03457d","DOIUrl":"https://doi.org/10.1039/d5sc03457d","url":null,"abstract":"Tailoring photocatalysts to achieve both strongly reductive and oxidative properties from a common scaffold remains challenging. Herein, we report the development of a pair of photocatalysts, isothiatruxene (ITS) and isosulfonyltruxene (ITSO2), by modulating the valence states of heteroatoms. ITS exhibits highly reducing power, facilitating selective cleavage of C-O bonds in biomass derivatives despite their negative redox potentials. Upon oxidation of ITS, the resultant ITSO2 demonstrates strongly oxidizing capacity, enabling metal-free and acid-free upcycling of plastic wastes even with their high redox potentials. By immobilizing ITS and ITSO2 on polystyrene and oxidized lignin supports, respectively, we have developed recyclable photocatalysts that drive multiple catalytic cycles with high efficiency. Gram-scale upcycling of plastic is achieved by integrating photoredox catalysis with flow chemistry. Mechanistic studies reveal that the excited states of ITS and ITSO2 can directly activate inert substrates, correlating with their strong redox properties. The newly introduced pair of photocatalysts, characterized by their metal-free nature, concise synthesis via trimerization, and dual photocatalytic capabilities encompassing both strongly reducing and oxidizing properties, show great potential for a wide range of applications. Furthermore, this study presents a sustainable catalytic strategy for synthesizing high-value aromatic compounds directly from biomass derivatives and plastic wastes.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677829","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":"Air-Processed, Ultraresponsive NIR Photodetectors Using 2D Perovskite Hybrids","authors":"Dulce Zugasti-Fernández, Priscila I. Román-Román, Mara Gutierrez-Avila, A. Paulina Gómora-Figueroa, Juan Hernández-Cordero, Vojtech Jancik, Norberto Hernandez-Como, Diego Solis-Ibarra","doi":"10.1039/d5sc02348c","DOIUrl":"https://doi.org/10.1039/d5sc02348c","url":null,"abstract":"Halide perovskites have shown tremendous potential as active materials in various optoelectronic devices, including solar cells, light-emitting diodes and photodetectors. However, their relatively large bandgaps –typically limited to ~1.40 eV (~885 nm)–constrain their use as near-infrared (NIR) photodetectors. Here, we present a novel two-dimensional (2D) hybrid perovskite (PDA)<small>₂</small>PbI<small>₄</small> (PDA = 6-phenyl-3,5-hexadiynylammonium), which upon thermopolymerization forms (<em>poly</em>-PDA) PbI<small>₄</small> (<em>poly</em>PDA = polymerized PDA). This material can be incorporated into NIR photodetectors that exhibit record-high responsivities of up 10<small>⁷</small>A/W and external quantum efficiencies of up to 144.4% at 980 nm under a 4 V biasAbstract text goes here. Notably, the devices can be fabricated, operated, and stored entirely under ambient air conditions, highlighting their stability and processability.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"32 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684986","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":"Helical foldamers replicating membrane-spanning gramicidin a with pH responsiveness and ultrafast potassium permeability","authors":"Jun Tian, Lei Zhang, Ze Lin, Shizhong Mao, Zeyuan Dong","doi":"10.1039/d5sc01362c","DOIUrl":"https://doi.org/10.1039/d5sc01362c","url":null,"abstract":"Structural simulation of natural ion channels remains a challenging topic. To fabricate artificial ion channels structurally resembling natural gramicidin A (gA), we prepared a type of precise hollow helical molecular channel by means of a modular synthesis strategy. Helical molecules are able to form 2.9 nm membrane-spanning channels through dimeric π-stacking assembly and efficiently accelerate ion transmembrane transport, with ultrahigh transport activity of up to 28 nM. Among these molecular channels with transmembrane structures similar to gA, one of them significantly exceeds natural gA for potassium ion transport, while another one exhibits the same proton transport activity as natural gA under identical conditions. Moreover, we found that the positive charges near the entrance of the channel reduce the potassium transport rate of the channel but significantly promote proton transport. In addition, a molecular channel with terminal amine groups shows pH-regulated ion transport function. This is the first example of structural replication of natural gA, in which helically folded molecules with assembled dimeric structure yield fantastic ion transport properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"110 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144677827","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}