Chemical Science最新文献_第3页

Linker desymmetrisation unlocks new topologies, defective clusters, and catalytic activity in zirconium- and rare-earth metal-organic frameworks 连接体不对称解锁新的拓扑结构，缺陷簇，和催化活性在锆和稀土金属有机框架

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05365j

Borja Ortín-Rubio, Yunhui Yang, Emilio Borrego-Marin, Jaume Rostoll-Berenguer, Carlos Vila, Judith Juanhuix, Inhar Imaz, Jorge A R Navarro, Daniel Maspoch

{"title":"Linker desymmetrisation unlocks new topologies, defective clusters, and catalytic activity in zirconium- and rare-earth metal-organic frameworks","authors":"Borja Ortín-Rubio, Yunhui Yang, Emilio Borrego-Marin, Jaume Rostoll-Berenguer, Carlos Vila, Judith Juanhuix, Inhar Imaz, Jorge A R Navarro, Daniel Maspoch","doi":"10.1039/d5sc05365j","DOIUrl":"https://doi.org/10.1039/d5sc05365j","url":null,"abstract":"Metal–organic frameworks (MOFs) based on highly connected nets continue to expand the landscape of reticular chemistry, with zirconium (Zr) and rare-earth (RE) clusters offering ideal nodes for the construction of robust and structurally diverse materials. While desymmetrisation of tetratopic linkers has recently emerged as a promising approach to accessing new framework topologies, the underlying principles governing cluster connectivity remain poorly understood. Here, we systematically investigate the effect of linker desymmetrisation on the assembly of Zr- and RE-MOFs. A literature survey of planar tetratopic linkers revealed that geometric parameters such as height-to-width ratio and torsion angles play a key role in dictating cluster connectivity. Guided by these insights, we designed two new nanosized tetratopic ligands with enhanced conformational flexibility, enabling the synthesis of six MOFs with diverse cluster types and topologies. These include three Zr-MOFs, two featuring 8-connected (8-c) Zr₆ clusters with csq and scu topologies, and one with a rare 4-c Zr cluster, and three RE-MOFs, including one with an unprecedented heptanuclear RE cluster forming a 4,8L15 net. Finally, we demonstrate that frameworks with accessible metal clusters, such as the csq-Zr-MOF and 4,8L15-RE-MOF, show outstanding catalytic activity in the hydrolysis of P–F bonds in G-type nerve agent simulants. These results highlight linker desymmetrisation as a powerful strategy for tuning both structure and function in MOFs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"21 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241802","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

Adsorption-Mediated Efficient Glucose Electrooxidation on Transition Metal Aerogels for Biomass Upgradation 过渡金属气凝胶吸附介导的高效葡萄糖电氧化用于生物质升级

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05524e

Haoxin Fan, Xiuming Bu, Ziqi Wan, Shougang Sun, Hengwei Lou, Xuemei Zhou, Jie Gao, Jiaojiao Miao, Jian Zhang, Wei Gao, Dan Wen

{"title":"Adsorption-Mediated Efficient Glucose Electrooxidation on Transition Metal Aerogels for Biomass Upgradation","authors":"Haoxin Fan, Xiuming Bu, Ziqi Wan, Shougang Sun, Hengwei Lou, Xuemei Zhou, Jie Gao, Jiaojiao Miao, Jian Zhang, Wei Gao, Dan Wen","doi":"10.1039/d5sc05524e","DOIUrl":"https://doi.org/10.1039/d5sc05524e","url":null,"abstract":"Electrocatalytic glucose oxidation reaction (GOR) to produce high value-added chemicals is facilitating the selective conversion and efficient utilization of biomass, while the oxidation products and reaction pathways associated with different transition metals remain insufficiently explored. Herein, the GOR performance on Co, Ni, and Cu metal aerogels were systematically investigated, exhibiting the activity order of Ni > Co > Cu for GOR electrocatalysis. Metal oxyhydroxides (M-OOH) from surface reconstruction of metal aerogels are identified as the actual active species, and the glucose adsorption strength on M-OOH correlated to the GOR property for metal aerogels are elucidated. In situ characterizations further revealed the interfacial reaction mechanism and reaction path on Ni aerogel with high activity and formic acid selectivity. Besides, the efficient GOR property of Ni aerogel further promoted stable water electrolysis at high current densities. Thus, this study offers constructive guidance for designing high-performance GOR electrocatalysts and establishes a feasible prototype for biomass upgradation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"101 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241610","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

Visible Light Photo-Switching in a Conformationally-Strained Electron Acceptor via a Dual Singlet-Triplet Mechanism 通过双单重态-三重态机制在构象应变电子受体中的可见光光开关

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc03702f

Sai Shruthi Murali, Aditi Kumar, Damon M. de Clercq, Céline Janiseck, Geoffrey Robert Weal, Isabella Wagner, Kai Chen, Michael P Nielsen, Timothy W Schmidt, Justin Hodgkiss, Paul Hume

{"title":"Visible Light Photo-Switching in a Conformationally-Strained Electron Acceptor via a Dual Singlet-Triplet Mechanism","authors":"Sai Shruthi Murali, Aditi Kumar, Damon M. de Clercq, Céline Janiseck, Geoffrey Robert Weal, Isabella Wagner, Kai Chen, Michael P Nielsen, Timothy W Schmidt, Justin Hodgkiss, Paul Hume","doi":"10.1039/d5sc03702f","DOIUrl":"https://doi.org/10.1039/d5sc03702f","url":null,"abstract":"Molecular photo-switches have significant potential for use in smart materials that can be controlled by light. Photo-switches function due to lowering or complete removal of the barrier to switching in the excited state. This constraint on the ground and excited state potential energy surfaces means that relatively few photo-switching molecules are known, and fewer that only utilise visible photons. Here, we report the unanticipated visible-light photo switching behavior of a conformationally strained electron acceptor molecule, NIDCS-A, which consists of an anthracene core linked via vinylic double bonds to two thiophene-naphthalamide substituents. Using a combination of spectroscopic techniques, we find that NIDCS-A exhibits an unusual dual photo-switching mechanism via both singlet and triplet excited states. In the singlet state, photoisomerisation precedes geometric relaxation, which enables the molecule to overcome a surprisingly large energy barrier. At later times, photoisomerisation is mediated by long-lived triplet states. We draw several lessons for future work. First, photo-switching of vibrationally excited molecules is able to outcompete geometry relaxation. Second, our work reveals intrinsic molecular ISC as a complementary strategy to intramolecular triplet energy transfer for triplet-mediated photo-switching. Finally, we suggest that NIDCS-A may provide a template for the construction of all-optical three state molecular photo-switches.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"57 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241619","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

Copper Pyrithione Complexes with Endoplasmic Reticulum Localisation Showing Anticancer Activity via ROS Generation 具有内质网定位的铜吡硫酮配合物通过ROS生成显示抗癌活性

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d4sc06628f

Atreyee Mishra, Dominic J. Black, Thomas S Bradford, Karrera Djoko, Benjamin J Hofmann, Jamie J Hunter, Rianne M. Lord, Robert Pal, Harvey James Smart, Tameryn Stringer, James William Walton

引用次数: 0

Expanded segments of three-dimensional carbonaceous nets with chirality: Synthesis and structures 具有手性的三维碳质网的扩展段：合成和结构

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc06999h

Toshiya M. Fukunaga, Kiyofumi Takaba, Satoshi Yoshida, Saori Maki-Yonekura, Koji Yonekura, Hiroyuki Isobe

引用次数: 0

Quenching Mechanism in Rotaxane Mechanophores: Insights from Acene-Based Luminophores 轮烷机械团的猝灭机制：来自丙烯酸基发光团的见解

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05343a

Keigo Nonaka, Hayato Sakai, Ryusei Mori, Naoki Shimada, Shunsuke Hatatsu, Taku Hasobe, Yoshimitsu Sagara

{"title":"Quenching Mechanism in Rotaxane Mechanophores: Insights from Acene-Based Luminophores","authors":"Keigo Nonaka, Hayato Sakai, Ryusei Mori, Naoki Shimada, Shunsuke Hatatsu, Taku Hasobe, Yoshimitsu Sagara","doi":"10.1039/d5sc05343a","DOIUrl":"https://doi.org/10.1039/d5sc05343a","url":null,"abstract":"Rotaxane-based mechanophores that exploit spatial separation between a luminophore and a quencher are attractive due to their high structural design flexibility, enabling high-contrast changes in fluorescence intensity. However, it remains unclear whether their quenching mechanism is predominantly governed by photoinduced electron transfer (PET) or ground-state charge-transfer (CT) complex formation. This study unveils the quenching mechanism using rotaxane mechanophores incorporating π-extended anthracene, tetracene, or pentacene. In toluene, the quenching efficiency decreases with increasing π-conjugation of the fluorophore. Steady-state and transient absorption spectroscopy clarify that the fluorescence quenching of the anthracene-containing rotaxane is primarily due to PET, with a minor contribution from CT complex formation. In contrast, no clear CT complex formation is observed for the tetracene- and pentacene-containing mechanophores. PET moderately quenches the fluorescence for the tetracene-based system, while the low PET efficiency in the pentacene-containing mechanophore results in minimal quenching. Polyurethane elastomer films containing the anthracene-based mechanophore exhibit a significant increase in fluorescence intensity upon mechanical deformation. In contrast, almost no activation is observed for the pentacene-based mechanophore embedded in polyurethane. These findings clarify that PET is the primary quenching mechanism in rotaxane-based mechanochromic mechanophores, offering valuable insights for the future design of supramolecular mechanophores.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"1 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241617","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

Exploring the Determination of The Standard Rate Constant in Electrochemical Metal Deposition: Theory and Experiment 探讨电化学金属沉积中标准速率常数的测定：理论与实验

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05636e

Rania Saad Guermeche, Abed Mohamed Affoune, Sabrina Houam, Imene Atek, Christine Vautrin-Ul, Mouna Nacef, Mohamed Lyamine Chelaghmia, Hubert Girault, Craig E. Banks, Ilhem Djaghout, Jacques Bouteillon, Jean Claude Poignet

{"title":"Exploring the Determination of The Standard Rate Constant in Electrochemical Metal Deposition: Theory and Experiment","authors":"Rania Saad Guermeche, Abed Mohamed Affoune, Sabrina Houam, Imene Atek, Christine Vautrin-Ul, Mouna Nacef, Mohamed Lyamine Chelaghmia, Hubert Girault, Craig E. Banks, Ilhem Djaghout, Jacques Bouteillon, Jean Claude Poignet","doi":"10.1039/d5sc05636e","DOIUrl":"https://doi.org/10.1039/d5sc05636e","url":null,"abstract":"A detailed investigation of the electrochemical metal deposition was carried out using both simulation and experimental cyclic voltammetry (CV). Kinetic curves were developed to relate peak-to-peak potential separation (ΔEp) to the cathodic charge transfer coefficient (α) and the standard rate constant (k0). From these curves, interpolation equations were derived to estimate k0, taking into account the effect of the transfer coefficients sum (α+β), whether equal to or different from 1. The validity of the equations was confirmed through the reduction of silver and rhenium ions in various electrolytes, yielding k0 values of 14.51×10-6 m s-1 for Ag⁺/Ag, 5.98×10-7 m s-1 for Cu⁺/Cu and 10.59×10-8 m s-1 for Re6+/Re. According to the Matsuda–Ayabe criteria for assessing electron-transfer reversibility, the Ag⁺/Ag and Cu⁺/Cu redox couples are regarded as quasi-reversible, while the Re⁶⁺/Re couple is classified as irreversible. The simulated CVs showed strong agreement with experimental results.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"57 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145255498","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

Visible-Light Induced Click Reactions of Acylsilanes with Pyruvate Electrophiles 可见光诱导的酰基硅烷与丙酮酸酯亲电试剂的咔嗒反应

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc06269a

Rowan L Pilkington, Rosa Kössler, Jesse Molloy, Stefan Bräse, Daniel L Priebbenow

引用次数: 0

Ligand-Controlled Divergent Enantioselective Hydroarylation of Cyclobutenes 配体控制的环丁烯发散性对映选择性氢芳基化

IF 8.4 1区化学

Chemical Science Pub Date : 2025-10-08 DOI: 10.1039/d5sc05740j

Renming Pan, Jie Zhu, Xinjie Zhou, Minyan Wang, Ping Lu

引用次数: 0

Enabling technology for accelerated discovery of supramolecular materials 加速发现超分子材料的技术