Chemical Science最新文献

{"title":"Pore Engineering in Metal–organic Frameworks and Covalent Organic Frameworks: Strategies and Applications","authors":"Shengqian Ma, Yanpei Song","doi":"10.1039/d5sc01635e","DOIUrl":"https://doi.org/10.1039/d5sc01635e","url":null,"abstract":"Crystalline porous materials, particularly metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), have garnered significant attention for advanced applications due to their tunable pore environments and versatile functionalities. By precisely controlling factors such as size, shape, functional sites, and pore distribution, MOFs and COFs can be tailored to exhibit high selectivity for specific molecules, making them ideal for applications in gas storage and separation, catalysis, and water remediation. This review provides a background overview, beginning with an introduction to pore surface engineering strategies and the design features of MOFs and COFs. It then highlights recent advancements in three key research areas that our group has investigated in-depth over the past decade, discussing the strategies and principles involved. Finally, we outline the remaining challenges and offer our perspectives on future opportunities for pore-engineered MOFs and COFs.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"65 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144288572","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":"Designing molecular qubits: computational insights into first-row and group 6 transition metal complexes","authors":"Arturo Sauza-de la Vega, Andrea Darù, Stephanie Nofz, Laura Gagliardi","doi":"10.1039/d5sc02544c","DOIUrl":"https://doi.org/10.1039/d5sc02544c","url":null,"abstract":"In the realm of optically addressable qubits, a previously synthesized and characterized Cr(<small>IV</small>) pseudo-tetrahedral complex, featuring four strongly donating ligands surrounding the chromium center, has demonstrated potential as a qubit candidate. This study proposes analogs of this complex through a metal substitution strategy, extending the investigation to different complexes based on metal centers selected from first-row and Group 6 transition metals. Computational modeling based on multiconfigurational methods CASPT2 and MC-PDFT was utilized to calculate energy gaps between ground and excited electronic spin states, and zero-field splitting parameters. Simulations were applied to each equilibrium geometry and related deformations based on vibrational modes. All results align with previous experimental findings, but also show that qubits based on V and Ti centers could be more electronically stable than the Cr one, suggesting a lower electronic features dependency from their related geometry. In some cases geometrical deformations provide changes in relative energy gaps between triplet and singlet excited state, that could potentially swap, offering a different initialization process, and some inspiration for ligand design based on such deformations. Additionally, this study identifies an unsynthesized Ti(<small>II</small>) compound as a promising candidate for molecular qubits. This finding highlights the role of computational multireference methods in the rational design of qubit systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"20 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144288573","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":"Novel lanthanide(III)/gallium(III) metallacrowns with appended visible-absorbing organic sensitizers for molecular near-infrared imaging of living cells","authors":"Timothée Lathion, Julie Bourseguin, Svetlana V. Eliseeva, Matthias Zeller, Stéphane Petoud, Vincent L. Pecoraro","doi":"10.1039/d5sc01320h","DOIUrl":"https://doi.org/10.1039/d5sc01320h","url":null,"abstract":"Optical imaging of biological samples in the near-infrared (NIR) domain is of major interest for non-invasive experiments due to reduced light scattering, absorption and autofluorescence. Taking advantage of the maleimide moieties in the [Ln<small>₂</small>Ga<small>₈</small>(shi)<small>₈</small>(mip)<small>₄</small>]<small>²⁻</small> metallacrowns (MCs; <strong>shi<small>³⁻</small></strong> = salicylhydroximate; mip<small>²⁻</small> = 5-maleimido-isophthalate; Ln = Nd<small>^III</small>, Gd<small>^III</small>, Er<small>^III</small>, Yb<small>^III</small> and Y<small>^III</small>), we appended visible-absorbing thiol-coumarin (<strong>C</strong>) sensitizers through a thiol-Michael addition click reaction, affording the functionalized [Ln<small>₂</small>Ga<small>₈</small>(shi)<small>₈</small>(C-mip)<small>₄</small>]<small>²⁻</small> MCs. By using this approach, the sensitization of NIR-emitting Nd<small>^III</small>, Er<small>^III</small> and Yb<small>^III</small> was achieved upon excitation in the visible range (<em>λ</em><small>_exc</small> = 420 nm) through the appended coumarins. NIR epifluorescence microscopy of living HeLa cells incubated with the Nd<small>^III</small> derivative confirmed unambiguous detection of the signal arising from the <small>⁴</small>F<small>_3/2</small> → <small>⁴</small>I<small>_11/2</small> electronic transition in the range of 1050–1080 nm in the cells. These results demonstrate that the [Ln<small>₂</small>Ga<small>₈</small>(shi)<small>₈</small>(mip)<small>₄</small>]<small>²⁻</small> MC can be used as a versatile molecule for tuning the chemical and photophysical properties of the [Ln<small>₂</small>Ga<small>₈</small>] MC family.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"70 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144268592","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 versatile NIR probe for multifunctional detection of tumors, fatty liver, and liver injury","authors":"Qihang Ding, Jiqiang Liu, Xinyue Zhang, Jun Li, Keith Man-Chung Wong, Amit Sharma, Pengfei Zhang, Quli Fan, Chao Yin, Hui Zhou, Tony D. James, Jong Seung Kim","doi":"10.1039/d5sc01433f","DOIUrl":"https://doi.org/10.1039/d5sc01433f","url":null,"abstract":"Abnormal viscosity, reduced pH, and elevated levels of superoxide anion (O<small>₂</small>˙<small>⁻</small>) in living cells are often associated with various biological dysfunctions and oxidative stress. Although some studies have reported probes capable of detecting one or two of these biomarkers, achieving simultaneous, rapid, and convenient detection of all three remains a significant challenge. Herein, we present a rhodamine based probe, <strong>DM301</strong>, which selectively activates fluorescence in three distinct channels in response to pH, viscosity, and O<small>₂</small>˙<small>⁻</small> respectively. Systematic spectroscopic analyses demonstrated <strong>DM301</strong>'s exceptional response to these biomarkers, while <em>in vitro</em> experiments confirmed its mitochondrial specificity at the cellular level. To validate the diagnostic potential of <strong>DM301</strong>, we employed various disease models, including 4T1 tumors, fatty liver, and drug-induced liver injury, all associated with these abnormal biomarkers. <em>In vivo</em>, experiments further established the safety of <strong>DM301</strong> and demonstrated its specificity to pH, viscosity, and O<small>₂</small>˙<small>⁻</small> across different pathological conditions in living organisms. We anticipate that these findings will offer practical and effective strategies for investigating the physiological roles of biomarkers and analytes in diverse biological systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"220 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144268593","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":"Correction: Collective motions in the primary coordination sphere: a critical functional framework for catalytic activity of the oxygen-evolving complex of photosystem II","authors":"Hiroshi Isobe, Takayoshi Suzuki, Michihiro Suga, Jian-Ren Shen, Kizashi Yamaguchi","doi":"10.1039/d5sc90135a","DOIUrl":"https://doi.org/10.1039/d5sc90135a","url":null,"abstract":"Correction for ‘Collective motions in the primary coordination sphere: a critical functional framework for catalytic activity of the oxygen-evolving complex of photosystem II’ by Hiroshi Isobe <em>et al.</em>, <em>Chem. Sci.</em>, 2025, https://doi.org/10.1039/d5sc02386f.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"9 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144268594","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":"Toward High-Selectivity CO2 Photoelectroreduction: Mechanistic Foundations, Recent Advances and Challenges","authors":"Guosheng Zhou, Zhenzhen Wang, Junjie Gong, Shijie Shen, Wenwu Zhong","doi":"10.1039/d5sc02284c","DOIUrl":"https://doi.org/10.1039/d5sc02284c","url":null,"abstract":"Photoelectrochemical carbon dioxide reduction reaction (PEC CO2RR) is a promising strategy for converting CO2 into high-value chemicals that contribute to carbon neutrality. However, CO2 reduction is often accompanied by a variety of competitive reaction paths in the actual reaction process, which may generate a variety of products. The selective regulation of different products not only directly affects the yield and separation cost of the target product, but also relates to the energy efficiency and economic feasibility of the whole process. Improving product selectivity is essential for increasing product yield and understanding reaction mechanism. This review systematically summarizes recent advances and challenges in achieving high selectivity in PEC CO2RR. Firstly, the basic concept and principle of PEC CO2RR are summarized. Next, the key factors affecting product selectivity are discussed, including catalyst design (catalyst type, modification, composition, morphology), reaction conditions (applied voltage, light intensity and wavelength, reaction temperature, electrolyte type) and reactor design (photoelectrode area, synergistic oxidation effect, geometric structure, gas diffusion electrode). In addition, kinetic and thermodynamic aspects such as the CO2 adsorption model, band gap structure, and reaction free energy are also explored. Then, the recent five years of research progress in different products is described in detail, focusing on the current status and challenges in the study of C1 products and C2 products. Subsequently, the primary factors leading to the failure of PEC CO2RR were summarized, and various cooperative strategies were introduced to achieve long-term stability in product selectivity. Finally, the challenges and future directions of developing PEC systems with enhanced selectivity are introduced. In particular, the importance of innovative catalyst design, reaction stability, reaction environment optimization, advanced equipment structure and reaction mechanism analysis for promoting PEC CO2RR in industrial applications is emphasized.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"589 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269108","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":"Topological Variety and Self-Sorting in Homo- and Heteroleptic PdnL2n Metallo-Supramolecular Assemblies","authors":"Laura Neukirch, Guido H. Clever","doi":"10.1039/d5sc03203b","DOIUrl":"https://doi.org/10.1039/d5sc03203b","url":null,"abstract":"A plethora of nanoscale PdnL2n-type architectures has been synthesized through the coordination-driven self-assembly of Pd(II) ions and organic bis-monodentate bridging ligands. While initially, the focus was on homoleptic structures, comprising one type of ligand per assembly, the field has recently shifted towards reducing symmetry in heteroleptic multicomponent assemblies, containing two or more disctinct ligands in defined positions. In parallel, the incorporation of functional moieties such as binding and catalytic sites, photoswitches and redox units has seen a steep development. While empirical data has been gathered on the relationship between ligand structure and assembly outcome for a limited number of cases, confidently forecasting the result of reacting a given ligand with Pd(II) cations often still remains challenging and has been mastered only for the simplest systems. Additionally, new PdnL2n topologies – along with subtle factors driving their formation (such as counter anion or guest templation and solvation effects) – are discovered continuously. For designing metallosupramolecular assemblies for application, it is of pivotal importance to increase predictabilty and gain control over assembly topology, as structure and properties are often closely connected. To raise awareness for the problem’s complexity, we commence this review by exploring the surprising breadth of topological diversity among homoleptic PdnL2n (n=2-8) architectures that has so far been found experimentally. We next discuss strategies for increasing the structural complexity even further through the non-statistical self-assembly of heteroleptic cages, the orientational self-sorting of asymmetric ligands, and chiral self-sorting effects. Special emphasis will be put on factors governing the particular self- assembly outcome as well as on rationalization approaches based on computations or geometrical considerations.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"30 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269082","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":"Dual-metal synergistic catalysis for promoting electrocatalytic CO2 reduction","authors":"Peng-Yu Shi, Yan Yan, Si-Yuan Yang, Jing-Jing Hao, Mei Wang, Tong-Bu Lu","doi":"10.1039/d5sc03193a","DOIUrl":"https://doi.org/10.1039/d5sc03193a","url":null,"abstract":"The increasing emphasis on carbon neutrality has driven significant research into the electrochemical CO<small>₂</small> reduction reaction (CO<small>₂</small>RR), aiming to convert CO<small>₂</small> into value-added chemicals and fuels. Dual-metal catalysts, known for their synergistic effects, have garnered considerable attention due to their enhanced electrocatalytic performance for the CO<small>₂</small>RR by providing more active sites and optimizing intermediate interactions. Herein, this review will comprehensively explore how the synergistic effect between the two metal centers embedded within atomic and nanoparticle dual-metal catalysts facilitates the electrocatalytic CO<small>₂</small>RR, elucidating the structure–activity correlations. Recent significant progress of dual-metal catalysts with synergistic effects for promoting electrocatalytic CO<small>₂</small> reduction will be summarized. Moreover, we will explore the design strategies of dual-metal catalysts and examine the influence of different types of metal active centers in the catalysts on the reaction pathway of the electrocatalytic CO<small>₂</small>RR, aiming to uncover profound insights for catalyst optimization and deepen mechanistic understanding of the catalytic process. Finally, the review identifies current research gaps and outlines future directions, emphasizing the need for innovative techniques to enhance catalytic stability and achieve multi-carbon products from the CO<small>₂</small>RR using dual-metal catalysts with synergistic effects. This topic could inspire extensive interest to further accelerate and explore the innovations of catalysts in energy conversion.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"22 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260569","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":"Employment of a C(sp3)-based nucleophile for photoinduced palladium-catalysed cross-coupling","authors":"Beom Ho Kim, Byeongdo Roh, Dong Jun Kim, Hong Geun Lee","doi":"10.1039/d5sc02325d","DOIUrl":"https://doi.org/10.1039/d5sc02325d","url":null,"abstract":"The development of efficient methods for C(sp<small>³</small>)–C(sp<small>³</small>) bond formation remains a longstanding challenge in synthetic chemistry, especially in palladium catalysis employing sterically bulky electrophiles. In this study, we present a novel approach for achieving C(sp<small>³</small>)–C(sp<small>³</small>) cross-coupling <em>via</em> photoinduced palladium catalysis, employing cyclopropanols as masked C(sp<small>³</small>)-nucleophiles. Leveraging the unique reactivity of photoexcited palladium, this protocol enables radical-mediated C(sp<small>³</small>)–C(sp<small>³</small>) coupling across a broad range of substrates including sterically hindered and functionally diverse alkyl halides under mild conditions. This method significantly expands the extent of palladium-catalysed cross-coupling for bond construction between sp<small>³</small>-hybridized carbon units, providing streamlined access to structurally complex C(sp<small>³</small>)-rich frameworks that are crucial for medicinal chemistry.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"586 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260567","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":"Multilayer graphene crystals with enhanced performances in oxygen reduction and zinc–air batteries via interlayer carbon promoted OO bond dissociation","authors":"Yongfang Qu, Qian Tang, Dandan Wang, Bing He, Yong Liu, Wei Chen, Guangtao Yu, Boyuan Tang, Fujian Liu, Liangti Qu","doi":"10.1039/d5sc02570b","DOIUrl":"https://doi.org/10.1039/d5sc02570b","url":null,"abstract":"O<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O bond activation determines activities of oxygen reduction reaction (ORR) catalysts, and developing metal-free catalysts that outperform precious metals remains challenging. Herein, we demonstrate the mechanochemical polymerization of pyrrole tandem carbonization for designing nitrogen-containing, micropore-penetrated multilayer graphene crystals (NM-MGCs) with abundant barrier-free nanochannels for O<small>₂</small>, leading to high exposure of carbon atoms adjacent to graphitic nitrogen. Due to the ordered multilayer structure with steady layer-by-layer van der Waals interaction, the resultant exposed interlayer carbon atoms exhibit much improved ability to activate O<small>₂</small> through adsorption-configuration-induced O<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O bond dissociation in the ORR with approximately zero energy barrier. Thus, the NM-MGCs show record-breaking ORR performance among metal-free catalysts, which can be fabricated as air cathodes for both flow and flexible Zn–air batteries, exhibiting high maximum power density, high specific capacity (815.30 mA h g<small>_Zn</small><small>⁻¹</small> at 5 mA cm<small>⁻²</small>), and extraordinary long-term cycling durability (&gt;800 h) and round-trip energy efficiency (63.7%). The overall performance of Zn–air batteries assembled using the NM-MGCs surpass those of commercial Pt/C (20 wt%) and many literature-reported metal and/or metal-free electrocatalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"23 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269109","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}