Chemical Science最新文献_第9页

On the Synthesis and Structure of Reactive Halonium Ions 反应性卤鎓离子的合成及结构研究

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-19 DOI: 10.1039/d5sc03756e

Lukas Fischer, Michael H. Lee, Anja Wiesner, Carsten Muller, Sebastian Riedel

{"title":"On the Synthesis and Structure of Reactive Halonium Ions","authors":"Lukas Fischer, Michael H. Lee, Anja Wiesner, Carsten Muller, Sebastian Riedel","doi":"10.1039/d5sc03756e","DOIUrl":"https://doi.org/10.1039/d5sc03756e","url":null,"abstract":"Fluorinated diethyl and dipropyl halonium salts, [Br(CH2CF3)2][WCA] 1Br, [I(CH2CHF2)2][WCA] 2I and [X(CH2CH2CF3)2][WCA] (X = Br 5Br, I 5I; WCA = [Sb(OTeF5)6]−), were synthesized via fluoroalkylation or oxidation of bromofluoro and iodofluoro alkanes. The molecular structures of 1Br and 2I, as well as a second different solid-state structure of the previously reported chloronium salt 1Cl, were determined by single-crystal X-ray diffraction. Additionally, the oxidation of 2-chloro-1,1,1-trifluoropropane CHCl(CH3)(CF3) led to the formation of a highly reactive compound that activates isobutane to form the tert-butyl cation [C4H9]+. Although the product could not be directly observed due to its thermal instability and low solubility, quantum-chemical calculations suggest the formation of an asymmetric chloronium ion with trifluoro n-propyl and isopropyl side chains.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319376","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

Crown ether–cycloparaphenylene hybrid multimacrocycles: insights into supramolecular gas sensing and biological potential 冠醚-环对苯乙烯杂化多巨环：洞察超分子气体传感和生物潜力

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-18 DOI: 10.1039/d5sc03476k

Yaning Hu, Tong Li, Taotao Su, Wudi Shi, Yabing Yu, Beibei Li, Meng-Hua Li, Sheng Zhang, Yuan-Qing Xu, Qi Liu, Di Wu, Youzhi Xu

{"title":"Crown ether–cycloparaphenylene hybrid multimacrocycles: insights into supramolecular gas sensing and biological potential","authors":"Yaning Hu, Tong Li, Taotao Su, Wudi Shi, Yabing Yu, Beibei Li, Meng-Hua Li, Sheng Zhang, Yuan-Qing Xu, Qi Liu, Di Wu, Youzhi Xu","doi":"10.1039/d5sc03476k","DOIUrl":"https://doi.org/10.1039/d5sc03476k","url":null,"abstract":"The topologically intriguing multimacrocyclic architecture is endowed with distinct physical and chemical properties. The synthesis of hybrid macrocycles combining crown ethers and cycloparaphenylenes (CPPs) presents a promising strategy for developing multifunctional supramolecular systems. Herein, we first report the precise construction of a series of crown ether–CPP hybrid multimacrocycles with enhanced photophysical properties and diverse host–guest interactions. Notably, the trimacrocyclic hybrid adopts a molecular tweezer-like conformation, resulting in a significantly higher fullerene binding affinity compared to the bismacrocycle. The fullerene complex showed improved conductivity and sensitivity with a limit of detection (LOD) of 19 ppb for NO2 with excellent cyclic stability and reliability. Additionally, the bismacrocycle exhibits significant cytotoxicity against cancer cell lines at low concentrations and enables fluorescence-based detection of inflammatory responses, highlighting its potential for biosensing applications. These findings underscore the versatility of crown ether–CPP hybrid macrocycles in supramolecular sensing and biochemistry, offering new avenues for the design of functional nanomaterials.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"45 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341444","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

All-photonic switching of a benzo[e]-fused dimethyldihydropyrene-azobenzene dyad in solid state for logic operations 用于逻辑运算的二甲基二氢芘-偶氮苯固体熔合物的全光子开关

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-18 DOI: 10.1039/d5sc02467f

Sariful Molla, Jakir Ahmed, Subhajit Bandyopadhyay

{"title":"All-photonic switching of a benzo[e]-fused dimethyldihydropyrene-azobenzene dyad in solid state for logic operations","authors":"Sariful Molla, Jakir Ahmed, Subhajit Bandyopadhyay","doi":"10.1039/d5sc02467f","DOIUrl":"https://doi.org/10.1039/d5sc02467f","url":null,"abstract":"Molecular switches offer high-precision tools for achieving photoresponsive control across a wide range of applications, from solar thermal energy storage systems to information processing. Molecular photoswitches are important components for the development of high-density memory devices and photonic information processing. A molecular photoswitch can generate at least two distinct states. Photochromic dyads of coupled photoswitches can attain more than two states if the two switches are independently addressable. However, orthogonal photoswitching in hybrid photochromic systems could be challenging. In this work, we discuss the development of two orthogonal hybrid photochromic dyads, integrating two distinct photoswitches: dimethyldihydropyrene (DHP) or benzo[e]-fused dimethyldihydropyrene (BDHP) with azobenzene. Despite the significant spectral overlap between these systems, careful design and selection of suitable light sources ranging from NIR to UV light have successfully decoupled the individual photoswitching processes. As a result, four well-characterized distinct states can be selectively controlled with light. We have constructed an all-photonic molecular logic gate by switching the system in thin film, showcasing the potential of these systems for advanced molecular information processing using the attenuated total reflectance (ATR)-based FTIR spectroscopy as the non-destructive readout mode.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"36 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144319382","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

Structural control of dynamic covalent cages: kinetic vs. thermodynamic assembly and PFAS removal from water. 动态共价笼的结构控制：动力学与热力学组装和PFAS从水中去除。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-06-18 DOI: 10.1039/d5sc02247a

Tobias Pausch, Pablo Martínez Mestre, Fabiola Zapata, Andreas Mix, Bernd M Schmidt

{"title":"Structural control of dynamic covalent cages: kinetic vs. thermodynamic assembly and PFAS removal from water.","authors":"Tobias Pausch, Pablo Martínez Mestre, Fabiola Zapata, Andreas Mix, Bernd M Schmidt","doi":"10.1039/d5sc02247a","DOIUrl":"10.1039/d5sc02247a","url":null,"abstract":"Dynamic covalent chemistry is a powerful tool to synthesise complex structures from simple building blocks. However, even minor variations in the numerous parameters governing self-assembly can drastically influence the size and structure of the resulting assemblies. Herein, we report the selective formation of three cages belonging to the low-symmetry Tri2 2Tri2 cage topology for the first time, using highly symmetric tritopic building blocks, confirmed by single-crystal X-ray (SC-XRD) analysis. Fluorinated and non-fluorinated aldehydes were combined with two amines differing in their degree of structural flexibility. Applying either kinetic or thermodynamic control through solvent selection allowed for the selective synthesis of either the low-symmetry Tri2 2Tri2 or the larger, highly symmetric Tri4Tri4 assemblies. While the fluorinated linker strongly preferred the formation of the Tri2 2Tri2 cage topology under thermodynamic control, the non-fluorinated linker selectively formed the Tri4Tri4 species. Kinetic control, using methanol as a poor solvent, allowed for the selective precipitation of the Tri2 2Tri2 intermediate. Reduction of the Janus-like fluorinated Tri2 2Tri2 cages yielded the cages Et2F2 red and TREN2F2 red, which showed high potential for removing perfluorooctanoic acid (PFOA) from water, with Et2F2 red exhibiting structural rearrangements in organic solvents to accommodate PFOA, as observed by 1H and 19F NMR titrations in combination with 19F DOSY measurements.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12188467/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504960","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

Isomer-dependent reactivity in the solid state: topochemical [4 + 4] vs. [4 + 2] cycloaddition reactions. 固体中依赖异构体的反应性：拓扑化学[4 + 4]与[4 + 2]环加成反应。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-06-18 DOI: 10.1039/d5sc02327k

Anu Lal, Kana M Sureshan

{"title":"Isomer-dependent reactivity in the solid state: topochemical [4 + 4] vs. [4 + 2] cycloaddition reactions.","authors":"Anu Lal, Kana M Sureshan","doi":"10.1039/d5sc02327k","DOIUrl":"https://doi.org/10.1039/d5sc02327k","url":null,"abstract":"This study investigates the reactivity of constitutional isomers of acylated N-hydroxybenzotriazole (HOBt) in solid-state photocycloaddition reactions. To understand the difference in solid-state reactivity of the isomers, we have synthesized two isomeric N- and O-acyl derivatives of HOBt via acylation with anthracene-9-carboxylic acid. Both O-anthr-9-oyl oxy-benzotriazole 1 and its N-acyl isomer 2 crystallized with the face-to-face arrangement of their anthracene units, with a separation of 3.8 Å between them, satisfying Schmidt's criteria, suggesting that they can undergo a topochemical [4 + 4] photocycloaddition reaction. Upon irradiation using blue light (456 nm), the isomer 2 underwent a quantitative [4 + 4] cycloaddition reaction yielding the dimer D2. However, isomer 1 did not undergo [4 + 4] cycloaddition; instead, it underwent a photochemical [4 + 2] cycloaddition with molecular oxygen, eventually yielding anthraquinone (AQ). The dimer D2 underwent a retro-cycloaddition reaction to revert back to the isomer 2. While isomers give the same product in solution-state reactions, our study establishes that isomers can react differently in the solid state and can give different products.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12208124/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144539158","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

Single-molecule contact switching via electro-inductive effects. 通过电感性效应的单分子接触开关。

IF 7.6 1区化学

Chemical Science Pub Date : 2025-06-18 DOI: 10.1039/d5sc02252e

Ya-Li Zhang, Tian-Hang Bai, Jing-Tao Ye, Li-Na Luo, Qiang Wan, Ju-Fang Zheng, Yong Shao, Ya-Hao Wang, Xiao-Shun Zhou

{"title":"Single-molecule contact switching via electro-inductive effects.","authors":"Ya-Li Zhang, Tian-Hang Bai, Jing-Tao Ye, Li-Na Luo, Qiang Wan, Ju-Fang Zheng, Yong Shao, Ya-Hao Wang, Xiao-Shun Zhou","doi":"10.1039/d5sc02252e","DOIUrl":"10.1039/d5sc02252e","url":null,"abstract":"The non-faradaic application of electric fields generated at the surface of charged electrodes to polarize bound molecules, also termed as electro-inductive effects, have recently attracted increasing attention in modifying the chemical reactivity of molecules in electrosynthesis. Herein, we applied this electro-inductive effect to control the Lewis adduct formation and dissociation between BF3 and pyridine N of heterocycles to realize single-molecule contact switching. In situ single-molecule conductance measurements, in situ Raman analysis and theoretical calculations clearly show that the outward electric field along the positively-charged electrode surface polarizes adsorbed molecules to withdraw electron density from the terminal pyridine N, which weakens the N-BF3 Lewis bond for dissociation upon applied positive potentials. The released unbounded pyridine N can connect the molecule into a molecular circuit for electron transfer (considered as the \"ON\" state). Meanwhile, the inward electric field along the negatively charged electrode surface promotes the formation of an N-BF3 Lewis bond, leading to breaking of the molecular circuit (considered as the \"OFF\" state). Combined with the optimization of BF3 concentration from the equilibrium BF4 - ⇌ BF3 + F-, the electro-inductive effect can reversibly switch single-molecule conductance in conductance measurements and tunnelling currents in I-V measurements.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":" ","pages":""},"PeriodicalIF":7.6,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12175611/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144332479","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

Iodide-mediated intermediate regulation strategy enables high-capacity and ultra-stable zinc–iodine batteries 碘离子介导的中间调控策略实现了高容量、超稳定的锌碘电池

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-18 DOI: 10.1039/d5sc03114a

Zhijie Xu, Jiaqi Yang, Peng Sun, Yaoyu Chen, Zhengxiao Ji, Xusheng Wang, Min Xu, Jinliang Li, Likun Pan

{"title":"Iodide-mediated intermediate regulation strategy enables high-capacity and ultra-stable zinc–iodine batteries","authors":"Zhijie Xu, Jiaqi Yang, Peng Sun, Yaoyu Chen, Zhengxiao Ji, Xusheng Wang, Min Xu, Jinliang Li, Likun Pan","doi":"10.1039/d5sc03114a","DOIUrl":"https://doi.org/10.1039/d5sc03114a","url":null,"abstract":"The practical implementation of aqueous zinc–iodine (Zn–I2) batteries is hindered by the limited cathode capacity, rampant Zn dendrite formation, and anode corrosion issues. In this work, we propose a novel iodide-mediated intermediate regulation strategy achieved through a rationally designed combination of zinc iodide (ZnI2) and high-loading cathodes. Mechanistic studies reveal that iodide ions (I−) generate abundant iodine active sites on the elemental iodine-embedded porous carbon cathode (I2@PAC), which facilitates the conversion of under-oxidized triiodide (I3−) to pentaiodide (I5−), thereby significantly enhancing cathode capacity. Concurrently, the I− coordinate with Zn2+ to suppress the decomposition of coordinated water molecules, effectively mitigating side reactions and enabling dendrite-free Zn deposition morphology. These mechanisms collectively contribute to exceptional Coulombic efficiency (>99.7%) and outstanding cycling stability. The optimized Zn–I2 full cell achieves a remarkable specific capacity of 250.2 mAh g−1 at 0.2 A g−1, along with ultralong cycling durability exceeding 10 000 cycles while maintaining 85% capacity retention. This iodide-mediated intermediate regulation strategy provides a viable pathway for developing high-capacity and ultra-stable aqueous Zn–I2 batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"19 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144341443","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

Novel particulate photocathode composed of CdTe-ZnTe solid solutions with a composition gradient for solar hydrogen evolution from water 具有组成梯度的CdTe-ZnTe固溶体组成的新型微粒光电阴极

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-17 DOI: 10.1039/d5sc02472b

Lionel Sebastian Veiga, Mamiko Nakabayashi, Takenori Fujii, Masakazu Sugiyama, Tsutomu Minegishi

{"title":"Novel particulate photocathode composed of CdTe-ZnTe solid solutions with a composition gradient for solar hydrogen evolution from water","authors":"Lionel Sebastian Veiga, Mamiko Nakabayashi, Takenori Fujii, Masakazu Sugiyama, Tsutomu Minegishi","doi":"10.1039/d5sc02472b","DOIUrl":"https://doi.org/10.1039/d5sc02472b","url":null,"abstract":"Particulate photoelectrodes are promising for the development of innovative unbiased water-splitting devices by combining a photoanode and a photocathode. This configuration relaxes the requirements for band edge potentials of oxygen- and hydrogen-evolution systems while enhancing the solar-to-hydrogen conversion efficiency. However, particulate photocathodes often exhibit lower performance than thin-film-based photocathodes because of the difficulty of implementing functional structures. In this study, a novel CdTe-based particulate photocathode prepared via the modified particle transfer method, along with a ZnTe contact layer introduced via the close-spaced sublimation method, is presented. A ZnxCd1−xTe (0 ≤ x ≤ 1) solid solution with a composition gradient is produced under the appropriate preparation conditions, and the conduction-band minimum gradient introduced by the composition gradient suppresses charge recombination and shifts the onset potential of the cathodic photocurrent to +0.7 VRHE. The introduction of a Cu layer to the back contact and post-deposition rapid thermal annealing further enhances the photocurrent, which reaches −7mA cm−2 at 0 VRHE and a half-cell solar-to-hydrogen efficiency of 1.1% at 0.28 VRHE. The photocathode also exhibits an incident photon-to-current conversion efficiency (IPCE) of 36% at 520 nm and greater than 10% IPCE across the wavelength range 440–800 nm, which is the highest IPCE reported thus far for a particulate photocathode. These findings demonstrate the potential of the method of introducing a composition gradient for enhancing photoelectrochemical and photocatalytic hydrogen evolution.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"183 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144304819","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

Asymmetric Intramolecular Reductive Coupling of Bisimines Templated by Chiral Diborons 手性二硼模板双亚胺的不对称分子内还原偶联

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-17 DOI: 10.1039/d5sc03633j

Tian Chen, Hao-Yang Wang, Ronghua Xu, Guangqing Xu, He Yang, Jiangtao Sun, Lung Wa Chung, Wenjun Tang

引用次数: 0

A nickel-catalysed radical mechanism by three-component dimensionality reduction strategies: a theoretical study 三组分降维策略下镍催化自由基机制的理论研究

IF 8.4 1区化学

Chemical Science Pub Date : 2025-06-17 DOI: 10.1039/d5sc03563e

Lin-Yan Bao, Rong-Wan Gao, Bo Zhu, Zhong-Min Su, Wei Guan

{"title":"A nickel-catalysed radical mechanism by three-component dimensionality reduction strategies: a theoretical study","authors":"Lin-Yan Bao, Rong-Wan Gao, Bo Zhu, Zhong-Min Su, Wei Guan","doi":"10.1039/d5sc03563e","DOIUrl":"https://doi.org/10.1039/d5sc03563e","url":null,"abstract":"Three-component coupling reactions represent a potent approach for synthesizing complex products. Radical-initiated three-component coupling reactions hold significant promise in synthetic chemistry but are often challenged by the high reactivity of radical species and the complex coordination environment of transition metal catalysts. Herein, we employed density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations to investigate the mechanism of three-component olefin difunctionalization. Our study reveals that the dimensionality reduction in multi-component coupling reactions is fundamentally governed by a metal-free radical–radical cycle mechanism. A concentration-driven coordination mode shift modulates the reactivity of the Ni(0) centre, thereby enabling the multi-component reaction to proceed with high selectivity. Pauli repulsion plays a decisive role in determining enantiomeric isomerism in the radical capture step during two-component cross-coupling. This work provides a theoretical comprehension for the rational design of efficient radical-mediated multi-component coupling reactions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144304714","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