Coordination Chemistry Reviews最新文献

Polyoxometalates (POMs), also known as transition metal‑oxygen clusters deliver unique physical and chemical properties such as low effective surface charge density, high thermal stability, and multi-electron acceptance, making them suitable for proton conductors. In recent years, proton conductive POMs have achieved significant progress in high performance (>10⁻² S/cm) comparable to conventional materials through structural regulation strategies. At the same time, the veiled conduction mechanism has been elucidated by structural analysis and characterization. In this review, the research of POMs (Keggin-type, Dawson-type, composite materials) in proton conduction is reviewed mainly from the design strategy, proton conductivity and mechanism, structure-function relationship, and application, finally with a detailed discussion of challenges and prospects. This review will provide more inspiration for exploring and applying proton-conducting POM materials.

As the saturation rate of the bulk polyolefin market accelerates, the development of high value-added polyolefins becomes increasingly urgent. Particular attention is directed towards advancing olefin block (co)polymers with innovative structures and functions, valued for their exceptional compatibility, mechanical properties, and solubility. The INFUSE from Dow Chemical has achieved significant success in both application market and basic research. Late transition metal catalysts exhibit distinctive advantages in synthesizing olefin block (co)polymers because of their unique chain walking properties. The present contribution outlines the progress achieved in well-defined olefin block (co)polymers using late transition metal catalysts. Categorized by the polymeric monomers, this review extensively summarizes and discusses catalyst structures, synthetic strategies, product features, and characterization methods for the block architecture. Metal complexes (Ni, Pd, Fe, Co, Ru) of α-diimine, amine-imine, amine-pyridine, bis(imino)pyridine, imine-monoxide, allyl-trifluoroacetate, dichloride and alkyl ligands have been employed to synthesize olefin block (co)polymers of ethylene, α-olefins, dienes, and cyclic olefins. Various synthetic strategies, including tandem living polymerization, chain shuttling polymerization, macromolecular cross-metathesis, and macromolecular coupling reaction are concluded. Gel permeation chromatography, nuclear magnetic resonance, and differential scanning calorimetry are frequently used techniques to confirm the block architecture by providing information on molecular weight, chain microstructure, and thermal properties, respectively. These fundamental properties of olefin block (co)polymers are compiled to support their application development. It is envisioned that future research on olefin block (co)polymers should prioritize the development of market-oriented products, which puts forward requirements on product performance characterization and application scenario expansion. Furthermore, investigating the relationship between catalyst structure, polymer microstructure, and product performance will effectively promote the commercialization process.

The emergence of multidrug resistance (MDR) pathogens and the rapid depletion of the antibiotic arsenal have sparked interest in discovering and developing innovative antimicrobial agents. One example of these new agents is antimicrobial nanostructured materials, which have received significant attention due to their intrinsic advantages and unique antibacterial mechanisms. Among such antimicrobial nanomaterials, carbon materials-based quantum dots (QDs), including graphene QDs (GQDs), graphene oxide QDs (GOQDs), and carbon QDs (CQDs), have a competitive edge due to their low cytotoxicity, ease of synthesis and modification, and highly uniform dispersibility in aqueous solutions. Carbon-based QDs can be prepared by “top-down” or “bottom-up” approaches, with tailorable properties and antimicrobial activity. The antibacterial properties of CQDs and GQDs, including ROS generation, bacterial membrane disruption, and interference with genomic DNA, have all been well described. For the first time, this review focuses on the emerging mechanisms for enhancing antibacterial effectiveness, such as antimicrobial phototherapy, enzymatic cascade activity, phytochemical therapy, and synergistic effects in combination with antimicrobial agents and herbal extracts for practical applications in bacterial detection and dressings for bacteria-infected wounds, ocular, periodontal, bone, and implant-related infections. Furthermore, the current challenges of carbon-based QDs are summarized, and their future promise for significantly improving treatment options instead of conventional methods against MDR bacteria is highlighted.

Persistent luminescence is an optical phenomenon where materials continue to emit light after the cessation of the excitation source which leads to different applications in areas like bioimaging, information storage, anticounterfeiting, etc. This review focuses on the latest advancements in near-infrared (NIR) persistent luminescence (PersL) materials doped with Cr³⁺, Mn⁴⁺, Mn²⁺, Fe³⁺ and Ni²⁺along with recent advances in the synthesis and mechanisms associated with the afterglow. A comprehensive discussion on the various types of defects and their importance in NIR PersL materials is also included, along with a section dedicated to the techniques used to characterize these defects and application of NIR PersL materials in different areas. The review also examines the different strategies to improve the NIR PersL. It starts with a brief description of the history of the PersL and then discusses the reported NIR PersL phosphors activated by manganese, chromium, iron and nickel ions. Understanding the mechanism associated with PersL is very important to develop a novel PersL phosphor, so the review discussed the role of defects and traps in PersL along with different models which include the conduction band model, oxygen vacancy model, and quantum tunneling model which is followed by few main applications of PersL materials and culminated by concluding and associated challenges and future directions in this ever-growing field.

A variety of emerging anticancer therapeutic strategies, including chemodynamic, photothermal and combination therapies, are igniting considerable interests due to their precise targetability, minimal side effects, high efficacy and simplified treatment procedures. Polyoxometalates (POMs), as typical metallodrugs, offer many advantages in cancer treatment, including simple synthesis processes, a defined and tunable structure, reversible redox properties, photo-thermal conversion capabilities, and acid-responsive aggregation features. This review focus on the application of POM-based therapeutic agents for cancer treatment. An overview of the broad applications of POM- based agents in chemotherapy, chemodynamic therapy, photothermal therapy and different combination therapies is provided, and insights into the corresponding mechanisms are elucidated. The interactions between POM-based materials and substrates in the tumor microenvironment are described in detail. Aiming at accelerating the practical applications of POMs-based anticancer agents, current challenges and the future directions are discussed.

Metal carbides are highly intriguing to researchers due to their diverse properties, including electrical, thermal, magnetic, and mechanical characteristics. They are prized for their high specific surface areas, exceptional biocompatibility, and versatile applications across various fields such as chemical synthesis, catalysis, mechanical components, coatings, electronics, and aerospace materials. Through techniques like photoelectron spectroscopy (PES) and density functional theory (DFT), scientists have extensively studied the geometries, microstructure, stability, charge distribution, electronic properties, and electromagnetic characteristics of metal carbide clusters. These studies have paved the way for the development of new metal−carbon materials at both atomic and macro scales, finding applications in industrial catalysis, high−temperature ceramics, electrode materials, supercapacitors, and even astrochemistry. This review delves into the compositions, methods for structure determination, bonding patterns, and geometric arrangements observed in a wide range of metal-carbide clusters. These clusters, composed of metal atoms bonded to carbon atoms in different ratios and configurations, have been thoroughly investigated to unravel their fundamental properties and potential applications. The goal of this review is to offer a comprehensive overview of our current understanding of the structural characteristics and chemical bonding within metal-carbide clusters, emphasizing their importance in materials science and catalysis. These insights are instrumental in designing novel nano−scale metal−carbide clusters that find utility in creating nanowires, nanotubes, and 2D sheets for various applications like photovoltaic cells, electrodes, batteries, catalysts, and electronic devices.

Alzheimer's disease (AD) is the predominant neurodegenerative disorder, affecting approximately 60–80 % of all patients diagnosed with dementia globally. Given the intricate nature of AD's pathogenesis, numerous biologically active substances have gained attention, including amyloid-β plaques (Aβ), TAU proteins, metal ions, and reactive oxygen/nitrogen/sulfur species. The development of small-molecule fluorescent probes targeting these molecules has emerged as a promising avenue for the diagnosis and treatment of AD. Despite significant progress, challenges remain in the field of AD-related fluorescent probes. One such challenge is achieving high selectivity and sensitivity towards the target biomolecules amidst the complex biological milieu. Furthermore, further investigation is required to address the probe stability, bioavailability, and biocompatibility issues in order to guarantee their efficacy in clinical applications. It is imperative that further innovation be pursued in the design and synthesis of fluorescent probes that are specifically tailored to AD. The integration of advanced imaging techniques, such as fluorescence imaging, may enhance the sensitivity and spatial resolution of these probes, facilitating early diagnosis and monitoring of disease progression. This review presents a systematic examination of the multifunctional fluorescent probes developed over the last five years, highlighting their structures, properties, and applications in targeted diagnosis and imaging of AD. By elucidating the probe design principles and mechanisms of action, we aim to provide insights into their potential applications in clinical research on AD.

The advent of nanoscience and technology has ushered in a realm of possibilities in photocatalysis research, offering transformative applications in energy and environmental sustainability. However, the practical utility of unmodified single semiconductor photocatalysts is hampered by limitations such as a restricted absorption spectrum, low intensity, unproductive recombination of photogenerated electrons and holes, and insufficient catalytic active sites. Among the myriad strategies reported in the literature, the construction of semiconductor heterojunctions emerges as exceptionally successful. This review delves into the rational design and development of efficient photocatalysts, focusing on the nuanced suppression of electrons and holes to facilitate enhanced redox reactions. Key elements explored include morphology control, the formation of diverse heterojunctions, the significance of synthesis methods, and the optimization of essential reaction parameters for hydrogen production. Addressing the broader landscape of challenges, the review not only delineates the advantages and limitations of these strategies but also provides practical insights and tips to overcome hurdles encountered during material synthesis and photocatalytic reactions. Through a comprehensive exploration of the intricacies involved, the review serves as a valuable guide for students and newcomers to the subject area. Moreover, this work transcends its immediate scope, offering new ideas, reasoned conclusions, and forward-looking proposals that aim to shape the trajectory of future research. It is not merely a compendium of knowledge but a catalyst that stimulates researchers working within the field and across interdisciplinary domains. As we navigate the intricate interplay of electrons and holes at the heterojunction interface, this review charts a course toward innovative solutions, ultimately propelling the field of photocatalysis into new frontiers.

Dye-sensitized photoelectrochemical cells (DSPECs), which consist an effective approach to achieve total water splitting, have attracted a lot of attention in recent years. Nowadays, most of the photosensitizers used in DSPECs are noble metal complexes, especially polypyridine‑ruthenium complexes. To avoid the use of noble metal ions, metal-free dyes are emerging as promising candidates for the construction of low-cost and environmentally friendly DSPECs, which have been greatly improved in recent years. The metal-free dyes, including perylene dyes, porphyrin/subporphyrin dyes, triphenylamine dyes, and other dyes, have been utilized in photoanode-based, photocathode-based and tandem DSPECs. This review aims at describing the current situation of metal-free dyes used in DSPECs and the relationships between dye structure and device efficiency, and then highlighting the essential role of the molecular design in dyes for the enhancement of durability and efficiency. Finally, the main challenges and their countermeasures are presented and some future opportunities are suggested.

The rapid growth of the high-tech industry has resulted in an unprecedented demand for rare earth elements (REEs) due to their unique and irreplaceable properties. However, the limited reserves and non-renewable nature of REEs have created a significant imbalance between supply and demand. Recycling and separation of REEs from various industrial and mining wastes are crucial in alleviating the supply pressure and promoting sustainable development. Recently, utilizing reticular materials for REE recovery has addressed considerable interest. These materials are noted for their high adsorption capacity, selectivity, and chemical stability, making them ideal candidates for efficient REE recycling. This review provides a brief overview of the design concepts and synthesis methods for chemically stable reticular materials, including metal-organic frameworks (MOFs), covalent organic frameworks (COFs), and hydrogen-bonded organic frameworks (HOFs). It then delves into recent advancements in the use of reticular materials for effective REE recovery, summarizing key aspects such as adsorption capacity, efficiency, and influencing factors. Additionally, it highlights the interaction mechanisms between reticular materials and REEs. Finally, it offers insights into the foundational challenges and future research directions. This review aims to contribute to the ongoing development and design of reticular materials for efficient REE recycling.