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Arene fluorination and trifluoromethylation enabled by tetravalent group 10 metals ('formally' NiIV, PdIV, PtIV) 四价10族金属实现芳烃氟化和三氟甲基化(‘正式’ NiIV、PdIV、PtIV)
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-07-15 Epub Date: 2026-03-11 DOI: 10.1016/j.ccr.2026.217739
Luca Demonti , Hana Tabikh , Noel Nebra
Organofluorine compounds, mainly those containing F itself or trifluoromethyls (−CF3) in arenes, are ubiquitous in pharma/agrochemical industries and material science, making them essential to the well-being of mankind. The metal-mediated aryl−Rf bond formations (Rf = F, CF3) are commonly hampered by multiple factors (low nucleophilicity of the F anion, strong M−CF3 bonds, difficult transmetallation, moisture sensitivity, etc.). Accordingly, the finding of synthetic schemes to build aryl−Rf bonds constitutes a major challenge in modern coordination/organometallic chemistry. This review seeks to critically summarize the most appealing approaches to aryl−F/CF3 couplings taking place from structurally characterized MIVRf species (M = Ni, Pd, Pt; Rf = F, CF3).
The concept of inverted ligand field (ILF) often displayed by some of the ‘formally’ MIVRf species compiled herein, together with spectroscopic and reactivity insights supporting the ILF electronic structure picture, is also introduced and briefly discussed.
有机氟化合物,主要是那些在芳烃中含有F本身或三氟甲基(- CF3)的化合物,在制药/农用化学品工业和材料科学中无处不在,对人类的福祉至关重要。金属介导的芳基- Rf键的形成(Rf = F, CF3)通常受到多种因素的阻碍(F−阴离子的低亲核性,强M−CF3键,难金属化,湿敏感性等)。因此,寻找构建芳基- Rf键的合成方案构成了现代配位/有机金属化学的主要挑战。这篇综述旨在批判性地总结最有吸引力的方法芳基- F/CF3偶联发生在结构表征的MIVRf物种(M = Ni, Pd, Pt; Rf = F, CF3)。本文还介绍并简要讨论了一些“正式”的MIVRf物种经常显示的倒置配体场(ILF)的概念,以及支持ILF电子结构图的光谱和反应性见解。
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引用次数: 0
Advances of light-activated cationic porphyrins and phthalocyanines for cancer photodynamic therapy 光活化阳离子卟啉和酞菁在癌症光动力治疗中的研究进展
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-07-15 Epub Date: 2026-03-11 DOI: 10.1016/j.ccr.2026.217821
Daiane N. Maronde , José E. Rodríguez-Borges , Leandro M.O. Lourenço
Cationic porphyrins (Por) and phthalocyanine (Pc) derivatives are photoactive compounds with strong absorption in the UV–Vis region, making them promising candidates for photodynamic therapy (PDT) against cancer cells. Due to less solubility properties of some compounds in aqueous environments, structural modifications are often required to enhance their amphiphilicity and bioavailability. Introducing positively charged groups, such as e.g., pyridinium or ammonium moieties, into the macrocyclic framework significantly improves water solubility and cellular uptake, optimizing their potential for the PDT approach. This review focuses on the recent advancements in the design and application of cationic Por and Pc dyes for PDT of cancer diseases. Several parameters of the different PDT studies with versatile molecules are analyzed and compared across different structural modifications, light absorption properties (Soret and Q bands), singlet oxygen quantum yield (Ф), fluorescence quantum yield (ФF), (photo)stability, and attending to the half-maximal inhibitory concentration (IC50). Additionally, the impact of metal insertion and the nature, number, and position of cationic substituents, peripheral or axial, are discussed in relation to their photodynamic performance. Emphasis is placed on structure activity relationships, the selective accumulation in tumor cells, subcellular localization, and phototoxicity under different light irradiation conditions. This review is distinguished by a critical and comparative assessment of the literature, addressing relevant gaps in previous studies, particularly the insufficient and non-systematic determination of key photophysical parameters. Notwithstanding this standpoint, this review underscores the central role of rational molecular design and structure–activity relationships, contributing significantly to the development of efficient and selective cationic photosensitizers and to the advancement of PDT as a minimally invasive and targeted therapeutic strategy.
阳离子卟啉(Por)和酞菁(Pc)衍生物是一种在紫外-可见区具有强吸收的光活性化合物,是抗癌光动力治疗(PDT)的有希望的候选者。由于某些化合物在水环境中的溶解度较低,通常需要进行结构修饰以提高其两亲性和生物利用度。在大环框架中引入带正电荷的基团,如吡啶或铵基团,可显著改善水溶性和细胞摄取,优化其用于PDT方法的潜力。本文综述了阳离子Por和阳离子Pc染料用于肿瘤PDT的设计和应用的最新进展。通过不同的结构修饰、光吸收特性(Soret和Q波段)、单线态氧量子产率(Ф∆)、荧光量子产率(ФF)、(光)稳定性和参加半最大抑制浓度(IC50),分析和比较了具有多用途分子的不同PDT研究的几个参数。此外,金属插入的影响和阳离子取代基的性质,数量和位置,外周或轴向,讨论了与其光动力性能的关系。重点介绍了结构活性关系、肿瘤细胞的选择性积累、亚细胞定位以及不同光照条件下的光毒性。本综述的特点是对文献进行了批判性和比比性评估,解决了先前研究中的相关空白,特别是关键光物理参数的不充分和非系统确定。尽管如此,本综述强调了合理的分子设计和结构-活性关系的核心作用,对高效和选择性阳离子光敏剂的开发以及PDT作为一种微创和靶向治疗策略的进步做出了重大贡献。
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引用次数: 0
Cyanine Nanoassemblies for synergistic cancer therapy: From aggregate-state modulation to Phototheranostic integration 协同癌症治疗的菁氨酸纳米组件:从聚集状态调节到光疗整合
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-07-15 Epub Date: 2026-03-11 DOI: 10.1016/j.ccr.2026.217783
Di Zhang , Shuheng Qin , Hai Xu , Hui Bian , Yuan-Yuan Zhao , Xiao Cheng , Jinrong Zheng , Xiaojun Peng , Juyoung Yoon
The unique photophysical properties of cyanine dyes—strong NIR absorption, large molar extinction coefficients, and flexible structural tunability—have positioned them as an important class of photosensitizers for photothermal therapy (PTT) and photodynamic therapy (PDT). However, free cyanine dyes suffer from intrinsic limitations, including poor stability, aggregation-caused quenching (ACQ), low ROS generation, and rapid clearance, which severely restrict their biomedical utility.
Recent advances in molecular self-assembly now offer powerful strategies to overcome these obstacles. Through π–π stacking, hydrophobic interaction, electrostatic association, peptide/protein templating, or metal-ion coordination, cyanine dyes can be organized into highly ordered nanostructures—such as J-aggregates, H-aggregates, nanomicelles, and hybrid nanoassemblies—with precisely tunable morphology and optical behavior. These nanoassemblies restrict conformational freedom, stabilize the excited state, suppress ACQ, and markedly enhance ROS yield and photothermal conversion. In particular, J-aggregates enable red-shifted and sharpened absorption bands, improving tissue penetration and energy utilization for deep-tissue phototherapy.
Beyond enhancing PDT/PTT performance, self-assembled cyanine nanostructures integrate naturally into multifunctional platforms capable of tumor targeting, tumor microenvironment (TME)-responsive activation, multimodal imaging, and combination therapy—such as PTT–PDT synergy, chemo-phototherapy, SDT, or immunotherapy. Despite these promising advances, challenges remain, including controlling assembly stability in vivo, achieving batch-to-batch reproducibility, and predicting biological fate in complex physiological environments.
This review summarizes recent progress in cyanine-dye self-assembly, with emphasis on assembly mechanisms, aggregate-state engineering, structure–property relationships, and strategies for improving PDT/PTT efficacy and combination cancer therapy. We further discuss existing limitations and future opportunities for translating assembled cyanine nanotherapeutics into precision oncology. Together, these insights highlight the power of supramolecular engineering in transforming traditional cyanine dyes into robust, versatile, and clinically meaningful phototheranostic nanoplatforms.
菁染料独特的光物理性质-强近红外吸收,大摩尔消光系数和灵活的结构可调性-使其成为光热治疗(PTT)和光动力治疗(PDT)的重要光敏剂。然而,游离花青素染料存在固有的局限性,包括稳定性差、聚集引起的猝灭(ACQ)、低ROS生成和快速清除,这严重限制了它们的生物医学应用。分子自组装的最新进展为克服这些障碍提供了强有力的策略。通过π -π堆叠、疏水相互作用、静电结合、肽/蛋白质模板或金属离子配位,花青素染料可以被组织成高度有序的纳米结构,如j聚集体、h聚集体、纳米胶束和杂化纳米组装体,具有精确可调的形态和光学行为。这些纳米组件限制了构象自由,稳定了激发态,抑制了ACQ,显著提高了ROS产率和光热转化率。特别是,j聚集体实现了红移和锐化的吸收带,提高了组织穿透和深层组织光疗的能量利用。除了增强PDT/PTT性能外,自组装的花青素纳米结构自然集成到多功能平台中,能够靶向肿瘤、肿瘤微环境(TME)响应激活、多模态成像和联合治疗,如PTT - PDT协同、化学光疗、SDT或免疫治疗。尽管取得了这些有希望的进展,但挑战仍然存在,包括控制体内组装的稳定性,实现批对批的可重复性,以及预测复杂生理环境中的生物命运。本文综述了花青素染料自组装的最新进展,重点介绍了组装机制、聚合状态工程、结构-性质关系以及提高PDT/PTT疗效和联合癌症治疗的策略。我们进一步讨论了将组装的菁氨酸纳米疗法转化为精确肿瘤学的现有限制和未来机会。总之,这些见解突出了超分子工程的力量,将传统的花青素染料转化为强大的,通用的,临床上有意义的光治疗纳米平台。
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引用次数: 0
Design mechanisms and biomedical applications of peptide-metal chelates in antimicrobial therapy, tumor theranostics, and integrated diagnosis-treatment systems 肽-金属螯合物在抗菌治疗、肿瘤治疗和综合诊断治疗系统中的设计机制和生物医学应用
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-07-15 Epub Date: 2026-03-11 DOI: 10.1016/j.ccr.2026.217819
Yusu Li , Xinyue Zhao , Jin-ao Duan, Ping Xiao
The growing global antimicrobial resistance crisis and limitations of conventional cancer therapies call for innovative biomedical strategies. Peptide-metal chelates are promising multifunctional biomaterials that leverage peptide-metal ion synergy to overcome traditional therapeutic bottlenecks, with core value in building integrated platforms for programmable targeted delivery, spatiotemporal smart responsiveness and intrinsic theranostic synergy. Research in this field has evolved from basic molecular discovery to systematic rational design and now clinical smart applications. This review presents a novel research and development roadmap for peptide-metal chelates, elaborating their design principles, structure-function mechanisms and latest biomedical advances. It highlights their unique “Trojan horse” strategy for antibacterial resistance and precise tumor targeting via the EPR effect and tumor microenvironmental triggers such as pH and enzymes. It details their applications in intelligent drug delivery, high-efficacy antimicrobial therapy, precision anticancer treatment, and theranostic platforms integrating imaging and therapy. Addressing gaps in existing fragmented summaries, including the lack of systematic design-synthesis-application integration and insufficient basic-clinical translation analysis, the review also notes unresolved challenges in long-term in vivo safety, bioavailability optimization and GMP-compliant large-scale production. Finally, it prospects core directions like AI-assisted rational molecular design, advanced multi-stimuli responsive materials and multimodal theranostic integration, which are expected to accelerate the clinical translation of peptide-metal chelates and offer innovative solutions for drug-resistant infections and refractory cancers.
日益严重的全球抗菌素耐药性危机和传统癌症治疗的局限性要求创新的生物医学策略。肽-金属螯合物是一种很有前途的多功能生物材料,利用肽-金属离子协同作用来克服传统的治疗瓶颈,其核心价值在于构建可编程靶向递送、时空智能响应和内在治疗协同的集成平台。这一领域的研究已经从基本的分子发现发展到系统的理性设计,再到现在的临床智能应用。本文综述了肽-金属螯合物的研究发展趋势,阐述了肽-金属螯合物的设计原理、结构功能机制和最新的生物医学进展。它突出了它们独特的“特洛伊木马”策略,通过EPR效应和肿瘤微环境触发因素(如pH和酶)实现抗菌耐药性和精确肿瘤靶向。详细介绍了其在智能给药、高效抗菌治疗、精准抗癌治疗、影像治疗一体化治疗平台等方面的应用。为了解决现有碎片化摘要的不足,包括缺乏系统的设计-合成-应用集成和基础-临床转化分析不足,该综述还指出了在长期体内安全性、生物利用度优化和符合gmp的大规模生产方面尚未解决的挑战。最后展望了人工智能辅助的理性分子设计、先进的多刺激响应材料和多模式治疗整合等核心方向,有望加速肽-金属螯合物的临床转化,为耐药感染和难治性癌症提供创新解决方案。
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引用次数: 0
Single-atom coordinated MXenes for organic pollutant detoxification: Mechanistic insights, challenges, and future directions 有机污染物解毒的单原子协调MXenes:机理见解、挑战和未来方向
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-07-15 Epub Date: 2026-03-11 DOI: 10.1016/j.ccr.2026.217809
K. Keerthi , E.A. Lohith , Sowjanya Vallem , K. Praveena , Dimpul Konwar , Kasibhatta Sivakumar , Rajenahally V. Jagadeesh , N.V.V. Jyothi , Aristides Bakandritsos , Sada Venkateswarlu , Minyoung Yoon , Radek Zboril
Organic pollutants, including plastics, pharmaceuticals, aromatic compounds, pesticides, and industrial solvents, pose a serious threat to soil quality, aquatic ecosystems, and human health. Single-atom-coordinated MXenes (SAs@MXenes) have emerged as promising platforms for detoxifying organic pollutants because of their tunable surface chemistry, high catalytic activity, and atomic-level precision. Anchoring isolated metal atoms on the MXene surface maximizes atom utilization and modulates the electronic structure, thereby improving charge separation, adsorption affinity, and redox reactivity. However, comprehensive reviews of this emerging class of SAs@MXenes catalysts for organic pollutant detoxification remain limited. This review summarizes diverse synthesis strategies for achieving stable single-atom dispersion, including defect engineering to anchor single atoms at vacancy sites, heteroatom coordination chemistry, axial coordination, the modulation of local electronic structure through ligand control, and UV-mediated synthesis that enables photochemical precision in atom placement. In addition, advanced characterization techniques are used to confirm atomic dispersion, oxidation states, and structural evolution, while electron paramagnetic resonance (EPR) spectroscopy provides insight into the reactive intermediates responsible for detoxification. Furthermore, SAs@MXenes function as both efficient catalysts and a robust adsorbents for the degradation and capture of organic contaminants. Computational approaches, including density functional theory (DFT), machine learning (ML), and molecular dynamics (MD) simulations, are emphasized to elucidate catalytic mechanisms, accelerate catalytic design, and clarify molecular-level interactions. Collectively, these strategies support the rational development of single-atom–coordinated MXenes for sustainable environmental detoxification, and their future perspectives are also presented.
有机污染物,包括塑料、药品、芳香族化合物、农药和工业溶剂,对土壤质量、水生生态系统和人类健康构成严重威胁。单原子配位MXenes (SAs@MXenes)由于其可调节的表面化学性质、高催化活性和原子级精度而成为有机污染物解毒的有前途的平台。将孤立的金属原子锚定在MXene表面可以最大限度地利用原子并调节电子结构,从而提高电荷分离、吸附亲和性和氧化还原反应性。然而,这类新兴的SAs@MXenes催化剂对有机污染物解毒的综合评价仍然有限。本文综述了实现稳定单原子分散的各种合成策略,包括缺陷工程将单原子锚定在空位上,杂原子配位化学,轴向配位,通过配体控制局部电子结构的调制,以及实现原子放置光化学精度的紫外线介导合成。此外,先进的表征技术用于确认原子弥散,氧化态和结构演变,而电子顺磁共振(EPR)光谱提供了对负责解毒的反应中间体的洞察。此外,SAs@MXenes作为有效的催化剂和强大的吸附剂,用于降解和捕获有机污染物。计算方法,包括密度泛函理论(DFT),机器学习(ML)和分子动力学(MD)模拟,强调阐明催化机制,加速催化设计,并阐明分子水平的相互作用。总的来说,这些策略支持单原子协调MXenes的合理发展,以实现可持续的环境解毒,并提出了它们的未来前景。
{"title":"Single-atom coordinated MXenes for organic pollutant detoxification: Mechanistic insights, challenges, and future directions","authors":"K. Keerthi ,&nbsp;E.A. Lohith ,&nbsp;Sowjanya Vallem ,&nbsp;K. Praveena ,&nbsp;Dimpul Konwar ,&nbsp;Kasibhatta Sivakumar ,&nbsp;Rajenahally V. Jagadeesh ,&nbsp;N.V.V. Jyothi ,&nbsp;Aristides Bakandritsos ,&nbsp;Sada Venkateswarlu ,&nbsp;Minyoung Yoon ,&nbsp;Radek Zboril","doi":"10.1016/j.ccr.2026.217809","DOIUrl":"10.1016/j.ccr.2026.217809","url":null,"abstract":"<div><div>Organic pollutants, including plastics, pharmaceuticals, aromatic compounds, pesticides, and industrial solvents, pose a serious threat to soil quality, aquatic ecosystems, and human health. Single-atom-coordinated MXenes (SAs@MXenes) have emerged as promising platforms for detoxifying organic pollutants because of their tunable surface chemistry, high catalytic activity, and atomic-level precision. Anchoring isolated metal atoms on the MXene surface maximizes atom utilization and modulates the electronic structure, thereby improving charge separation, adsorption affinity, and redox reactivity. However, comprehensive reviews of this emerging class of SAs@MXenes catalysts for organic pollutant detoxification remain limited<strong>.</strong> This review summarizes diverse synthesis strategies for achieving stable single-atom dispersion, including defect engineering to anchor single atoms at vacancy sites, heteroatom coordination chemistry, axial coordination, the modulation of local electronic structure through ligand control, and UV-mediated synthesis that enables photochemical precision in atom placement. In addition, advanced characterization techniques are used to confirm atomic dispersion, oxidation states, and structural evolution, while electron paramagnetic resonance (EPR) spectroscopy provides insight into the reactive intermediates responsible for detoxification. Furthermore, SAs@MXenes function as both efficient catalysts and a robust adsorbents for the degradation and capture of organic contaminants. Computational approaches, including density functional theory (DFT), machine learning (ML), and molecular dynamics (MD) simulations, are emphasized to elucidate catalytic mechanisms, accelerate catalytic design, and clarify molecular-level interactions. Collectively, these strategies support the rational development of single-atom–coordinated MXenes for sustainable environmental detoxification, and their future perspectives are also presented.</div></div>","PeriodicalId":289,"journal":{"name":"Coordination Chemistry Reviews","volume":"559 ","pages":"Article 217809"},"PeriodicalIF":23.5,"publicationDate":"2026-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147388422","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
Molecularly imprinted polymers: applications, computational approaches, and the transformative role of artificial intelligence 分子印迹聚合物:应用、计算方法和人工智能的变革作用
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-07-15 Epub Date: 2026-03-11 DOI: 10.1016/j.ccr.2026.217808
Parinaz Mofazali , Minoosh Lalinia , Jeffrey D. Gross , Ali Samadi
The review examines molecularly imprinted polymers (MIPs) technology and its potential applications to present current scientific progress in the field. It highlights that MIPs production at an industrial scale faces difficulties because different types of intermolecular interactions and polymerization conditions and material performance create complex synthesis challenges. Emphasis is placed on the versatility of MIPs in environmental monitoring, the food industry, extraction, sensors, drug delivery, and biomedicine, with the discussion on the integration of MIPs pointing out the possibilities for enhancing accuracy and reliability. Furthermore, combining MIPs with analytical and computational methods creates new opportunities for qualitative and quantitative evaluation. In this light, the application of artificial intelligence (AI) to improve MIP performance, expedite polymerization procedures, and forecast ideal monomer-template interactions is expanding. This manuscript offers a fresh viewpoint using combined MIP applications in biosensing, drug delivery, environmental treatment, food safety, and catalysis with AI-driven strategies. It also aims to establish a framework for the future development of the next generation of smart and sustainable technologies.
本文综述了分子印迹聚合物(MIPs)技术及其潜在应用,介绍了当前该领域的科学进展。它强调了工业规模的MIPs生产面临的困难,因为不同类型的分子间相互作用和聚合条件以及材料性能带来了复杂的合成挑战。重点介绍了MIPs在环境监测、食品工业、提取、传感器、药物输送和生物医学方面的多功能性,并讨论了MIPs的集成,指出了提高准确性和可靠性的可能性。此外,将MIPs与分析和计算方法相结合,为定性和定量评估创造了新的机会。在这种情况下,人工智能(AI)在改善MIP性能、加快聚合过程和预测理想单体-模板相互作用方面的应用正在扩大。这篇手稿提供了一个新的观点,使用联合MIP应用在生物传感,药物输送,环境处理,食品安全和催化与人工智能驱动的策略。它还旨在为下一代智能和可持续技术的未来发展建立一个框架。
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引用次数: 0
Advances in transition metal sulfides: Synthesis, properties, and modification strategies for electrocatalysis and energy conversion applications 过渡金属硫化物的研究进展:电催化和能量转换应用的合成、性质和改性策略
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-07-15 Epub Date: 2026-03-11 DOI: 10.1016/j.ccr.2026.217797
Rui Wang , Xingqiao Deng , Bo Hu , Mule Vijayalakshmi , Hui Tang , Liang He , Xuemeng Liu , Ch. Venkata Reddy , Kakarla Raghava Reddy , Jaesool Shim , Tejraj M. Aminabhavi
Transition metal sulfides (TMSs) are compounds composed of sulfur anions and one or more transition metal cations. They are characterized by having multiple crystal phases and electronic structures, including metallic, semiconducting, and insulating states. These tunable and controllable polycrystalline phases and electronic structures endow TMSs with unique physical and electrochemical properties, making them highly promising for energy-sector applications. Even though significant progress has been made in this field, most studies remain confined to idealized systems with only half-reactions, lacking a systematic understanding of the relationship between the intrinsic properties of materials and catalytic mechanisms, and ignoring the essential differences between half-reactions and complete reaction systems. To fully exploit the potential advantages of TMSs, it is necessary to clarify their mechanism of action in different catalytic processes systematically to establish a clear correlation between structural characteristics, intrinsic properties, and catalytic activity to gradually shift from qualitative studies focusing on single half-reactions to full-reaction application research in order to promote their practical development at the industrial and commercial scales. This review systematically summarizes recent advances in TMS-based electrocatalysts, covering preparation methods, structural features, and modification strategies, to establish a framework for rational structural design. Then elucidates the key electrocatalytic mechanisms that correlate catalytic performance with structural characteristics, thereby guiding the development of efficient catalysts. Finally, the review critically evaluates the application of TMS-based electrocatalysts in energy conversion devices beyond isolated half-reaction studies, identifies current challenges in practical implementation and commercialization, and outlines potential directions for future development.
过渡金属硫化物(tms)是由硫阴离子和一个或多个过渡金属阳离子组成的化合物。它们的特点是具有多种晶体相和电子结构,包括金属态、半导体态和绝缘态。这些可调谐和可控的多晶相和电子结构赋予tms独特的物理和电化学性能,使其在能源领域的应用前景非常广阔。尽管在这一领域取得了重大进展,但大多数研究仍然局限于只有半反应的理想体系,缺乏对材料内在性质与催化机理之间关系的系统理解,忽视了半反应与完全反应体系之间的本质区别。为了充分发挥tms的潜在优势,有必要系统地阐明其在不同催化过程中的作用机理,明确其结构特征、内在性质和催化活性之间的关系,逐步从专注于单一半反应的定性研究转向全反应的应用研究,以促进其在工业和商业规模上的实际发展。本文从制备方法、结构特点、改性策略等方面系统地综述了近年来基于tms的电催化剂的研究进展,以期建立合理的结构设计框架。然后阐明了将催化性能与结构特征相关联的关键电催化机理,从而指导高效催化剂的开发。最后,本文批判性地评估了基于tms的电催化剂在能量转换装置中的应用,确定了目前在实际实施和商业化方面的挑战,并概述了未来发展的潜在方向。
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引用次数: 0
Progress of naphthalene diimides crystalline hybrid networks in design and applications 萘二亚胺晶体杂化网络的设计与应用进展
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-06-01 Epub Date: 2026-02-12 DOI: 10.1016/j.ccr.2026.217696
Zi-Xin You , Ting Zhang , Qing-Lin Guan , Chao Zhang , Ming-Dong Zhou , Xing-Jing Zhang , Yong-Heng Xing
Stimuli-responsive inorganic–organic frameworks (IOFs) are a class of functional materials, can controllably respond to one or more external stimuli. Among various organic linkers employed in IOF design, naphthalene diimides (NDIs) are of great interest because of their rigid and planar structure, electron-deficient character, and tunable electronic properties. The NDI derivatives are suitable for applications in optoelectronics, photochromic displays, electrochromic devices, chemical sensing, and rewritable media. In spite of the progress made recently in the synthesis of NDI-based ligands, NDI derivatives remain underexplored in crystalline hybrid materials (CHNs) due to synthetic challenges. This review comprehensively summarizes advances in NDI-CHNs, with a focus on highlighting structure–function relationships, as well as emerging functionalities, thereby offering theoretical insight and practical guidance for future research.
刺激响应型无机有机骨架(IOFs)是一类能对一种或多种外界刺激做出可控反应的功能材料。在IOF设计中使用的各种有机连接剂中,萘二酰亚胺(ndi)因其刚性和平面结构、缺电子特性和可调谐的电子特性而备受关注。NDI衍生物适用于光电子、光致变色显示器、电致变色器件、化学传感和可重写介质等领域。尽管近年来在NDI基配体的合成方面取得了一些进展,但由于合成方面的挑战,NDI衍生物在晶体杂化材料(CHNs)中的开发仍然不足。本文综述了NDI-CHNs的研究进展,重点介绍了NDI-CHNs的结构-功能关系,以及新兴功能,从而为未来的研究提供理论见解和实践指导。
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引用次数: 0
Ether-oxygen based covalent organic frameworks: a new cognitive guide 基于醚氧的共价有机框架:一种新的认知指南
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-06-01 Epub Date: 2026-02-05 DOI: 10.1016/j.ccr.2026.217632
Yihong Mo , Yulu Chen , Haifu Zhang , Wenhai Feng , Fengxue Duan , Huhai Chen , Zhuoxi Su , Xiaofei Chen , Yifa Chen , Ya-Qian Lan
Ether‑oxygen based covalent organic frameworks (EO-COFs) represent an emerging class of porous crystalline materials that uniquely integrate the dynamic flexibility of ether‑oxygen (EO) bonds with the structural order of covalent organic frameworks (COFs). Compared to other COFs, EO-COFs exhibit remarkable structural adaptability, excellent chemical and thermal stability, and versatile post-modification compatibility, owing to tunable conformation and robust electronic nature of the C-O-C linkages. Since their first report in 2015, EO-COFs have demonstrated considerable application potential in multiple fields, including adsorption/separation, catalysis, chemical sensing, and energy storage, etc. These materials not only inherit the flexibility of EO polymers but also significantly enhance the porosity and crystallinity of COFs, thereby expanding their functionality and application scope. However, critical knowledge gaps persist in EO-COFs research, particularly in establishing quantitative structure-performance correlations, innovating low-cost synthetic pathways, and tailoring materials for advanced application fields. Therefore, this review will systematically summarize the preparation methods, properties, and application prospects of EO-COFs and discuss the development opportunities and challenges. We anticipate this review will stimulate more perspectives and new ideas for developing advanced functionalities and expanding regimes of EO-COFs.
基于醚氧的共价有机框架(EO-COFs)代表了一类新兴的多孔晶体材料,它独特地将醚氧(EO)键的动态灵活性与共价有机框架(COFs)的结构顺序结合在一起。与其他COFs相比,EO-COFs具有显著的结构适应性,优异的化学和热稳定性,以及多种修饰后的相容性,这是由于C-O-C键具有可调节的构象和强大的电子性质。自2015年首次报道以来,EO-COFs在吸附/分离、催化、化学传感和储能等多个领域显示出相当大的应用潜力。这些材料不仅继承了EO聚合物的柔韧性,而且显著提高了COFs的孔隙度和结晶度,从而扩大了COFs的功能和应用范围。然而,在EO-COFs研究中,关键的知识差距仍然存在,特别是在建立定量结构-性能相关性,创新低成本合成途径以及为高级应用领域定制材料方面。因此,本文将系统总结EO-COFs的制备方法、性能及应用前景,并探讨其发展机遇与挑战。我们期待这一综述将为开发先进功能和扩展EO-COFs机制激发更多的观点和新思路。
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引用次数: 0
Non-metallic ion batteries beyond convention: fundamentals, material innovations, and pathways to sustainable energy storage 超越传统的非金属离子电池:基本原理、材料创新和可持续能源储存途径
IF 23.5 1区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-06-01 Epub Date: 2026-02-05 DOI: 10.1016/j.ccr.2026.217666
Sadia Muzammal , Awais Ahmad , Tahir Rasheed , Muhammad Usman , Abdullah Aitani , Franics Verpoot , Abid Ali , Arfaa Sajid , N.A.S. Amin
The global shift towards renewable energy sources necessitates the progress of safe, sustainable, and high-performance energy storage technologies. Traditional metal-ion batteries, although dominant in current applications, face significant limitations, including resource scarcity, high costs, environmental impact, and safety risks. In response, non-metal ion batteries (NMIBs) have emerged as a promising class of energy storage systems that utilize non-metallic charge carriers, including protons (H+), hydronium (H3O+), ammonium (NH4+), halide ions (Cl, Br), and organic ions, as alternatives to metal ions. These systems offer numerous advantages, including fast ion diffusion, biocompatibility, design flexibility, and a reduced ecological footprint. This review presents a comprehensive overview of NMIBs, detailing their fundamental working principles, classification, electrode and electrolyte materials, electrochemical performance, and the distinct mechanisms underlying their operation. Special emphasis is placed on recent advances in advanced functional materials, such as MXenes, MOFs, and redox-active organics, that enhance ionic conductivity and cycle stability. The review also outlines current challenges and research gaps while providing strategic insights into the future direction of this emerging field. By highlighting the potential of NMIBs as viable successors to traditional technologies, this work contributes to the broader vision of achieving sustainable and scalable energy storage solutions.
全球向可再生能源的转变需要安全、可持续和高性能的能源存储技术的进步。传统金属离子电池虽然在当前的应用中占主导地位,但面临着资源稀缺、成本高、环境影响和安全风险等重大限制。作为回应,非金属离子电池(NMIBs)已经成为一种有前途的储能系统,它利用非金属电荷载体,包括质子(H+)、水氢离子(h30 +)、铵离子(NH4+)、卤化物离子(Cl−、Br−)和有机离子,作为金属离子的替代品。这些系统具有许多优点,包括快速离子扩散、生物相容性、设计灵活性和减少生态足迹。本文综述了NMIBs的基本工作原理、分类、电极和电解质材料、电化学性能及其不同的工作机制。特别强调了先进功能材料的最新进展,如MXenes, mof和氧化还原活性有机物,它们可以增强离子电导率和循环稳定性。该综述还概述了当前的挑战和研究差距,同时为这一新兴领域的未来方向提供了战略见解。通过强调nmib作为传统技术可行继承者的潜力,这项工作有助于实现可持续和可扩展的储能解决方案的更广泛愿景。
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Coordination Chemistry Reviews
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