Chemical Science最新文献_第6页

Design and Synthesis of Macrocycles with Tuneable Diameters and Helical Foldamers with Customizable Peripheral Side Chains 具有可调谐直径的大环和具有可定制外围侧链的螺旋折叠环的设计与合成

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-06 DOI: 10.1039/d5sc04138d

Saquib Farooq, Aurelien Crochet, Andreas F.M. Kilbinger

{"title":"Design and Synthesis of Macrocycles with Tuneable Diameters and Helical Foldamers with Customizable Peripheral Side Chains","authors":"Saquib Farooq, Aurelien Crochet, Andreas F.M. Kilbinger","doi":"10.1039/d5sc04138d","DOIUrl":"https://doi.org/10.1039/d5sc04138d","url":null,"abstract":"Tubular structures with nanosized pores have shown remarkable applications in areas such as ion transport and water filtration, but their development is often hindered by challenges including low yields, limited functionalization, and poor uniformity. Herein, we present a new series of macrocycles with tuneable diameters and helical foldamers featuring customizable peripheral side chains. The macrocycles, with diameters ranging from 0.8 to 1.4 nm, were synthesized in moderate to good yields using a one-pot method. Solid-state analysis revealed that these macrocycles form nanochannels, highlighting their potential applications in areas such as molecular recognition and artificial water channels (AWCs). Additionally, we synthesized helical aromatic amide polymers with narrow dispersities via a living chain-growth process. Our strategy enables the incorporation of diverse functional groups, including ethers, esters, acids, and amides, on the outer surfaces of the macrocycles or synthetic nanotubes. Circular dichroism (CD) spectroscopy confirmed the helical conformations of the polymers in solution. These macrocycles and foldamers present exciting opportunities for designing bioinspired membrane channels and functional nanotubes with tuneable hydrophobicity and cavity sizes, paving the way for innovative applications in nanotechnology and materials science.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"6 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229030","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

Seeing the Unseen: Spatio-temporal Visualization of Reactive Carbocation Intermediates in Electrolytic Cells 看到看不见的：电解电池中活性碳正离子中间体的时空可视化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-06 DOI: 10.1039/d5sc06447c

Abhijit Nandy, Barsha Pathak, Bikash Ranjan Isaac, Vijayamohanan K. Pillai, Shibdas Banerjee

引用次数: 0

Cooperative Fe-Ti dual-metal sites for highly efficient photocatalytic non-oxidative methane conversion 协同铁钛双金属位用于高效光催化非氧化甲烷转化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-06 DOI: 10.1039/d5sc05677b

Qingyun Zhan, Xiaowei Mu, Yuxiang Kong, Zhenlu Li, Le Liu, Yumeng Qian, Shuyan Song, Lu Li

{"title":"Cooperative Fe-Ti dual-metal sites for highly efficient photocatalytic non-oxidative methane conversion","authors":"Qingyun Zhan, Xiaowei Mu, Yuxiang Kong, Zhenlu Li, Le Liu, Yumeng Qian, Shuyan Song, Lu Li","doi":"10.1039/d5sc05677b","DOIUrl":"https://doi.org/10.1039/d5sc05677b","url":null,"abstract":"Selective methane conversion is a promising low-carbon technology, yet developing catalysts capable of effectively activating inert C–H bonds under mild conditions remains challenging. Here, we designed Fe2+-□-Ti4+ dual-metal-sites on the high-activity {012} facets of defective ilmenite (Fe1-xTiO3-x-NS). Mechanistic studies revealed that Fe2+-□-Ti4+ can be excited to form a long-lived Fe3+-□-Ti3+ active state, while surface lattice oxygen stabilizes the reaction intermediates during multistep elementary reactions. This bimetal–oxygen synergistic strategy significantly reduces the activation barrier for C–H bond cleavage to just 0.15 eV, fully block the over-dehydrogenation of methyl intermediates, and facilitate C–C bond formation, thereby achieving a favorable non-oxidative methane conversion rate that even surpasses noble metal-supported photocatalysts, with nearly 100% C2+ selectivity. This bimetallic-center construction strategy provides an efficient and economical pathway for methane conversion, exhibiting high catalytic activity and product selectivity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"28 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229078","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

Nonlinear Current Stimulation Unlocks High-Performance Zn-Mn Batteries via Reversible Phase Transformation 非线性电流刺激通过可逆相变解锁高性能锌锰电池

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-06 DOI: 10.1039/d5sc06137g

Yang Song, Haidong Zhong, Tingting Hu, Jun Du, Changyuan Tao, Qian Zhang

{"title":"Nonlinear Current Stimulation Unlocks High-Performance Zn-Mn Batteries via Reversible Phase Transformation","authors":"Yang Song, Haidong Zhong, Tingting Hu, Jun Du, Changyuan Tao, Qian Zhang","doi":"10.1039/d5sc06137g","DOIUrl":"https://doi.org/10.1039/d5sc06137g","url":null,"abstract":"The intrinsic complexity of reactions in Zn–Mn batteries constrain their practical deployment, necessitating precise control over dissolution and deposition processes. Here, we employ a stepwise evolution of current signals—from steady-state constant current through symmetric and asymmetric sine waves to chaotic regimes—to systematically interrogate the coupling between nonlinear electrical signals and electrode reactions. Remarkably, chaotic currents enhance the reversible transformation between Zn4SO4·(OH)6·nH2O (ZSH) and ZnxMnO(OH)2 (ZMO), revealing for the first time a direct correlation between waveform nonlinearity and electrochemical modulation. This ZSH/ZMO interconversion, alongside Zn2+/H+ insertion and extraction, underpins the cathodic reaction mechanism. Accumulation of inactive ZSH/ZMO phases emerges as the primary factor driving kinetic decay. Following seven cycles of chaotic activation, Zn–Mn batteries exhibit improved capacity, rate performance and cycling stability. The approach translates to flexible cells, delivering 92.23 mAh·g-1 with 76.37% retention after 1550 cycles at 1 A·g-1. In situ visualization, SEM imaging, and comprehensive thermodynamic and dynamic analyses reveal that nonlinear current stimulation reconstructs fractal mass transport pathways within the electrode, thereby optimizing ion pathways and structural stability. This study bridges nonlinear circuit dynamics and Zn–Mn electrochemistry, presenting a promising strategy to high-performance aqueous Zn–Mn batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"52 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235486","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

Over 260-folds Enhancement of Reverse Intersystem Crossing by a Host-guest Exciplex for a Multiple Resonance Emitter toward Efficient Narrowband Electroluminescence 多共振发射极主-客耦合体对高效窄带电致发光的260倍以上反向系统间交叉增强

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-06 DOI: 10.1039/d5sc05928c

Zetian Wang, Ting Li, Yongjun Song, Dajun Zhuang, Sen Yang, Lei He

{"title":"Over 260-folds Enhancement of Reverse Intersystem Crossing by a Host-guest Exciplex for a Multiple Resonance Emitter toward Efficient Narrowband Electroluminescence","authors":"Zetian Wang, Ting Li, Yongjun Song, Dajun Zhuang, Sen Yang, Lei He","doi":"10.1039/d5sc05928c","DOIUrl":"https://doi.org/10.1039/d5sc05928c","url":null,"abstract":"Multiple resonance (MR) thermally-activated delayed fluorescence (TADF) emitters hold great potential for fabricating high-efficiency narrowband organic lightemitting diodes (OLEDs) toward high-definition display applications. However, their slow reverse intersystem crossing (RISC) causes strong device efficiency roll-offs. Reported strategies to enhance the RISC rates (k RISC ) of MR-TADF emitters are based on chemical modification of the emitters, which complicates molecular design and synthesis and easily causes widened emission spectra. Here, by utilizing a delicately designed host-guest exciplex, the k RISC of a MR-TADF emitter is significantly enhanced without sacrificing the narrow emission bandwidth. By closely aligning the energy levels of the host and MR-TADF guest, the host-guest 3 exciplex state is efficiently formed, which serves as an intermediate triplet state to largely accelerate the RISC of the guest. By embedding a S/Se heavy atom into the host, the heavy atom is directly involved into the 3 exciplex state, which markedly strengthens the spin-orbital coupling and boosts the RISC. With the above strategy, host materials for a typical MR-TADF emitter (DtBuCzB) are designed and synthesized. The formed host-guest exciplex significantly boosts the k RISC of DtBuCzB by over 260-folds to 2.2×10 6 s -1 , while the emission color and narrow emission bandwidth are both preserved. Narrowband OLEDs using the hosts and DtBuCzB guest show maximum external quantum efficiencies (EQEs) up to 28.7% and EQEs at 1000 cd m -2 (EQE 1000 ) up to 23.3%, with the EQE 1000 values being the highest among non-sensitized narrowband OLEDs based on DtBuCzB reported so far.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145235489","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 focus on salts dissolved in salts: ionic liquid mixtures – ion pairs, ion pairing and ionic liquids 重点研究溶解在盐中的盐：离子液体混合物——离子对、离子对和离子液体

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-06 DOI: 10.1039/d5sc90213d

Tom Welton

引用次数: 0

Observation of shuttling on the one-second timescale in a [10]cycloparaphenylene/C60 [2]catenane [10]环对苯醚/C60[2]链烷在1秒时间尺度上的穿梭观察

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc05734e

Fabian M. Steudel, Clara Sabrià, Massimo Delle Piane, Ferran Feixas, Xavi Ribas, Giovanni M. Pavan, Max von Delius

{"title":"Observation of shuttling on the one-second timescale in a [10]cycloparaphenylene/C60 [2]catenane","authors":"Fabian M. Steudel, Clara Sabrià, Massimo Delle Piane, Ferran Feixas, Xavi Ribas, Giovanni M. Pavan, Max von Delius","doi":"10.1039/d5sc05734e","DOIUrl":"https://doi.org/10.1039/d5sc05734e","url":null,"abstract":"[2]Catenanes comprising two identical binding sites are an excellent platform to study the kinetics of non-covalent interactions. In this work, we show that the “shuttling” of the [10]CPP nanohoop between two identical fullerene bis-adduct binding sites occurs with regioisomer-dependent rates of 1–5 s-1 at room temperature, placing these among the slowest π-π and dispersion-based shuttling processes reported to date. The catenanes were accessed via Glaser–Eglinton macrocyclization from fullerene bis-adduct precursors, which were purified by extensive recycling chromatography, and characterized by variable-temperature 1H NMR spectroscopy. Molecular dynamic simulations employing well-tempered metadynamics closely reproduce the experimental activation barrier (ΔG‡ ca. 70 kJ mol-1), offering insight into the nanohoop’s motion and metastable states along the shuttling pathway. The kinetic data were further complemented by thermodynamic binding studies between [10]CPP and different fullerene bis-adduct regioisomers.These findings expand our understanding of the kinetics and thermodynamics of concave/convex π–π interactions and will inform the design of future mechanically interlocked machines and 2D materials with slow response to external stimuli.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"105 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215932","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

Mimicking sMMOH chemistry: trapping the Sc3+-bound nonheme FeIII–O–O–FeIII adduct prior to its conversion into an FeIV2(μ-O)2 core 模拟sMMOH化学：在转化为FeIV2(μ-O)2核之前捕获Sc3+结合的非血红素feii - o - o - feiii加合物

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc05667e

Patrick M. Crossland, Bittu Chandra, Saikat Banerjee, Chase S. Abelson, Yisong Guo, Marcel Swart, Lawrence Que

{"title":"Mimicking sMMOH chemistry: trapping the Sc3+-bound nonheme FeIII–O–O–FeIII adduct prior to its conversion into an FeIV2(μ-O)2 core","authors":"Patrick M. Crossland, Bittu Chandra, Saikat Banerjee, Chase S. Abelson, Yisong Guo, Marcel Swart, Lawrence Que","doi":"10.1039/d5sc05667e","DOIUrl":"https://doi.org/10.1039/d5sc05667e","url":null,"abstract":"Di-iron systems that activate O2 to form high-valent, oxo-bridged FeIV2 or FeIIIFeIV products are of great interest to bio-inorganic chemists due to their relevance to the chemistry of soluble methane mono-oxygenase (sMMOH), which incorporates both atoms of O2 gas into a diiron(IV) complex with an Fe2O2 diamond core. In this study, the [FeIII2(Me3NTB)2(μ-O)(μ-O 2)]2+ adduct (Me3NTB = tris((1-methyl-1H-benzo[d]imidazole-2-yl)methyl)amine) reacts with two Sc3+ to break the O–O bond that in turn forms the target FeIV(μ-O)2FeIV product. This study provides the first evidence that a Lewis acid can interact directly with a diferric-peroxo complex to initiate O–O bond cleavage, as evidenced via vibrational and X-ray absorption spectroscopy.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"102 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209871","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

N-heterocyclic carbenes as clickable molecular anchors for electrochemical surface functionalization of metals and glassy carbon n -杂环碳烯作为金属和玻璃碳电化学表面功能化的可点击分子锚

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc03908h

Antoine Juneau, Ahmadreza Nezamzadeh, Béatrice Laberge, Anastasia Messina, Justin Lomax, Thilini M. Suduwella, Jashanpreet Kaur, Vikram Singh, Mark D. Aloisio, Paul J. Ragogna, Cathleen M. Crudden, Janine Mauzeroll

{"title":"N-heterocyclic carbenes as clickable molecular anchors for electrochemical surface functionalization of metals and glassy carbon","authors":"Antoine Juneau, Ahmadreza Nezamzadeh, Béatrice Laberge, Anastasia Messina, Justin Lomax, Thilini M. Suduwella, Jashanpreet Kaur, Vikram Singh, Mark D. Aloisio, Paul J. Ragogna, Cathleen M. Crudden, Janine Mauzeroll","doi":"10.1039/d5sc03908h","DOIUrl":"https://doi.org/10.1039/d5sc03908h","url":null,"abstract":"The potential of alkyne-containing NHCs as anchor molecules for electrochemical surface modification is investigated. Using a combination of X-ray photoelectron spectroscopy, atomic force microscopy, fluorescence tagging, and shell-isolated nanoparticle-enhanced Raman spectroscopy, we demonstrate that these NHCs can bind effectively to multiple surfaces and be functionalized via electrochemical copper-catalyzed azide–alkyne cycloaddition. Notably, we extend the scope of substrates beyond metals by demonstrating successful modification of glassy carbon. Compared to diazonium salts, NHC coatings show comparable resistance to sonication while forming films of only ∼4 nm in thickness. This reduced film thickness leads to lower surface passivation, which could offer advantages for electrochemical applications. The versatility of these NHC as molecular anchors is demonstrated through the attachment of electrochemically active TEMPO˙, the immobilization of streptavidin, and the formation of copper coatings. These findings highlight the potential of NHCs as alternatives to thiols and diazonium salts for the design of functional materials, electrodes, and biosensors.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"37 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209873","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

Isomeric decker metallo-supramolecules with tunable luminescence and chiroptical properties 具有可调发光和热性的同分异构体双层金属超分子

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-03 DOI: 10.1039/d5sc04596g

Ningxu Han, Jianjun Ma, Hao Yu, Junjuan Shi, Manman Dai, Ziteng Guo, Zinuo Gao, Houyu Zhang, Ming Wang

{"title":"Isomeric decker metallo-supramolecules with tunable luminescence and chiroptical properties","authors":"Ningxu Han, Jianjun Ma, Hao Yu, Junjuan Shi, Manman Dai, Ziteng Guo, Zinuo Gao, Houyu Zhang, Ming Wang","doi":"10.1039/d5sc04596g","DOIUrl":"https://doi.org/10.1039/d5sc04596g","url":null,"abstract":"The regulation of interchromophoric interactions in multichromophoric systems is crucial for developing high-performance photofunctional materials. In this study, we present a novel self-assembly strategy to construct isomeric decker complexes, denoted as S1 and S2, which integrate disparate chromophores, achiral BODIPY and chiral binaphthyl moieties. This isomerization results in distinct chromophore packing modes. In the case of S1, the BODIPY and binaphthyl moieties are arranged in a relatively loose manner (~ 6.0 Å), enabling efficient FRET and preserving the strong locally excited (LE) emission (ΦF = 91.3%) characteristic of the BODIPY unit. In contrast, for S2, the denser packing between the BODIPY and binaphthyl moieties (~ 4.8 Å) leads to through-space charge transfer (TSCT) and weak charge transfer (CT) emission (ΦF = 8.6%). Notably, only complex (R)/(S)-S1 shows mirror-image circular dichroism (CD) signals based on chirality transfer and circularly polarized luminescence (CPL), as supported by TD-DFT calculations which reveal that the binaphthyl moiety alter the angle between the electric transition dipole moment (μ) and the magnetic transition dipole moment (m).","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"214 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209872","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