IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-10-03 DOI: 10.1016/j.cjsc.2025.100758

Jisung Yoon , Junghum Park , Hojae Lee , Sang won Lee , Miju Ku , Junseop Lee , Jonghyuck Lee , Tae ho Shin , Young-Beom Kim

Metal-supported solid oxide fuel cells (MS-SOFCs) have recently gained significant attention as an advanced SOFC technology, owing to their excellent mechanical robustness, ease of handling, and high manufacturability. The use of metal substrates enables improved durability under thermal and redox cycling, and allows for thinner electrolyte layers, contributing to enhanced performance. However, their fabrication typically requires high-temperature sintering to ensure adequate material properties and adhesion, as most SOFC components are ceramic. These high-temperature processes can lead to undesirable effects, including metal support oxidation, chemical side reactions, and accelerated particle growth, which degrade cell performance. This study introduces an ultra-fast sintering approach for MS-SOFC fabrication by directly integrating stainless-steel metal supports with nickel-yttria-stabilized zirconia (Ni-YSZ) composite anode active layers. The application of flash light sintering—an innovative ultra-fast technique—effectively suppressed Ni catalyst particle growth, expanding the electrochemical reaction area while minimizing material diffusion between the metal support and anode layer. As a result, the fabricated cells achieved a stable open-circuit voltage (OCV) exceeding 1 V at 650 °C and a peak power density of 412 mW/cm², representing an approximately 426.3% performance improvement over conventionally sintered cells. This research presents a transformative strategy for SOFC manufacturing, addressing the challenges of conventional long-duration heat treatments and demonstrating significant potential for advancing energy conversion technologies.

金属支撑固体氧化物燃料电池（ms -SOFC）作为一种先进的SOFC技术，由于其优异的机械稳健性、易于操作和高可制造性，最近受到了广泛的关注。金属基板的使用可以提高热循环和氧化还原循环下的耐久性，并允许更薄的电解质层，有助于增强性能。然而，它们的制造通常需要高温烧结以确保足够的材料性能和附着力，因为大多数SOFC组件是陶瓷的。这些高温过程可能导致不良影响，包括金属载体氧化、化学副反应和加速颗粒生长，从而降低电池性能。本研究介绍了一种超快速烧结方法，通过将不锈钢金属支架与镍钇稳定氧化锆（Ni-YSZ）复合阳极活性层直接集成，制造MS-SOFC。闪光烧结是一种创新的超快速技术，它有效地抑制了Ni催化剂颗粒的生长，扩大了电化学反应面积，同时最大限度地减少了金属载体和阳极层之间的材料扩散。结果表明，制备的电池在650°C下具有超过1 V的稳定开路电压（OCV）和412 mW/cm2的峰值功率密度，比传统烧结电池的性能提高了约426.3%。这项研究提出了SOFC制造的变革战略，解决了传统长时间热处理的挑战，并展示了推进能量转换技术的巨大潜力。

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引用次数: 0

Chiral europium-organotin oxo-clusters with dual-emission circularly polarized luminescence 具有双发射圆偏振发光的手性铕-有机锡氧簇

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-10-21 DOI: 10.1016/j.cjsc.2025.100759

Gui-Xin Yan , Er-Xia Chen , Jin-Xia Yang , Jian Zhang , Qipu Lin

Chiral metal-organic clusters (MOCs) integrating lanthanide ions (Ln³⁺) and organic luminophores present a promising platform for modulating circularly polarized luminescence (CPL). However, achieving dual-wavelength CPL in discrete cluster systems constitutes a considerable challenge. Herein, two enantiomeric pairs of heterometallic Eu–Sn oxo clusters, designated as Sn₂EuL₂-R/S and Sn₂EuL₄-R/S, were strategically synthesized using axially chiral binaphthol-phosphonate ligands. These hybrid clusters exhibit dual emission, characterized by a broad ligand-derived fluorescence band superimposed with sharp, characteristic Eu³⁺ f-f transitions, which enables excitation-dependent luminescence color tuning. Their emission profiles and quantum yields are found to be exquisitely adjusted by the distinct coordination environments of Sn⁴⁺ centers. Notably, Sn₂EuL₂-R/S demonstrates CPL activity in both near-UV (|g_lum| = 1.7 × 10⁻³) and visible (|g_lum| = 3.1 × 10⁻²) regions. This work not only reports the first instance of dual-wavelength CPL in a lanthanide/tin oxo complex but also establishes a robust design strategy for fabricating color-tunable chiral photonic materials.

整合镧系离子（Ln3+）和有机发光团簇的手性金属-有机团簇（MOCs）为圆偏振发光（CPL）调制提供了一个很有前景的平台。然而，在离散集群系统中实现双波长CPL构成了相当大的挑战。本文采用轴向手性双萘酚膦酸盐配体，合成了两个对映体对铕-锡氧杂金属簇，分别命名为Sn2EuL2-R/S和Sn2EuL4-R/S。这些杂化团簇表现出双重发射，其特点是配体衍生的荧光带与尖锐的特征Eu3+ f-f跃迁叠加在一起，从而实现了依赖于激发的发光颜色调谐。它们的发射谱和量子产率被Sn4+中心不同的配位环境巧妙地调整。值得注意的是，Sn2EuL2-R/S在近紫外（|glum| = 1.7 × 10−3）和可见光（|glum| = 3.1 × 10−2）区域均显示CPL活性。这项工作不仅报道了双波长CPL在镧系/锡氧配合物中的第一个实例，而且为制造可调颜色的手性光子材料建立了一个强大的设计策略。

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引用次数: 0

Ultrathin transparent metal-organic framework-based nanocomposite membranes for antibacterial wound healing 用于抗菌伤口愈合的超薄透明金属-有机框架纳米复合膜

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-09-26 DOI: 10.1016/j.cjsc.2025.100749

Zhiqi Hu , Lingling Wu , Duo Zhang , Yixue An , Jiao Wang , Binbin Zhao , Robert Chunhua Zhao , Rong Cao , Xue Yang

Metal-organic frameworks (MOFs) hold great promise for wound healing applications due to their high surface area, tunable pore structures, and tailored functionalities. However, a significant challenge lies in transforming pristine MOFs powders into ultrathin and flexible dressings that are compatible with soft biological systems. The current limitations of MOFs in practical usability and versatility hinder their integration into advanced wound dressings. Herein, we integrate MOF (ZIF-8) with an ultrathin cellulose membrane to form MOF-based matrix membranes (MMMs) that exhibit high transparency, exceptional mechanical stability, and satisfactory antimicrobial functionality for effective bacterial wound healing. The resulting MMMs can be fabricated into multifunctional dressings of various shapes and sizes, optimized for tissue applications, while maintaining excellent water-vapor permeability and patient compliance. Both in vitro and in vivo experiments demonstrated that the MMMs exhibit outstanding biocompatibility, antibacterial activity, and antioxidant properties, significantly accelerating the healing of bacterial-infected wounds. This work presents a transformative approach to wound care, establishing a foundation for next-generation dressings that combine the multifunctionality of MOFs with the mechanical and biological compatibility required for clinical applications.

金属有机框架（mof）由于其高表面积、可调孔结构和定制功能而在伤口愈合应用中具有很大的前景。然而，一个重大的挑战在于将原始mof粉末转化为与软生物系统兼容的超薄柔性敷料。目前MOFs在实用性和多功能性方面的局限性阻碍了它们集成到高级伤口敷料中。在此，我们将MOF （ZIF-8）与超薄纤维素膜结合，形成MOF基基质膜（MMMs），该膜具有高透明度，卓越的机械稳定性和令人满意的抗菌功能，可用于有效的细菌伤口愈合。由此产生的mm可以制成各种形状和尺寸的多功能敷料，针对组织应用进行了优化，同时保持良好的水蒸气渗透性和患者依从性。体外和体内实验表明，MMMs具有出色的生物相容性、抗菌活性和抗氧化性能，可显著加速细菌感染伤口的愈合。这项工作提出了一种革命性的伤口护理方法，为将mof的多功能与临床应用所需的机械和生物相容性相结合的下一代敷料奠定了基础。

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引用次数: 0

Thermochromic luminescence in low-dimensional antimony halide for detection of trace amount of water and anti-counterfeiting 低维卤化锑热致变色发光技术用于微量水的检测和防伪

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-09-24 DOI: 10.1016/j.cjsc.2025.100734

Hong-Zhao Zan , Hai-Xin Zhao , Xi-Gui Gao , Xiao-Zhong Wang , Yun-Zhi Zhu , Guo-Kun Li , Xu-Yang Yao , Chen Li , Xiang-Wen Kong , Xiao-Wu Lei

Stimuli-responsive luminescent switching materials with multifunctional properties are highly essential for advanced photonic applications, yet achieving such capabilities in halide perovskites continues to pose a significant challenge. In this work, we explore a new water-stimuli-responsive zero-dimensional (0D) Sb-based halide of [PhPz]₂SbCl₇·2H₂O (PhPz = phenylpiperazine), which consists of isolated [SbCl₆]^3⁻ octahedra in [PhPz]²⁺ cationic matrix with guest H₂O molecules. Under UV excitation, [PhPz]₂SbCl₇·2H₂O emits intense broadband red light with maximum emission at 645 nm, and combined optical characterization and theoretical calculations confirm that this luminescence originates from self-trapped excitons (STEs). Interestingly, the free water molecules can reversibly leave and entry the crystal lattice during heating-cooling cycles accompanied by the formation of dehydrated phase, which displays strong yellow emission with maximum peak at 580 nm. Therefore, reversible luminescent switching between red and yellow emission is achieved through controllable removal and adsorption process of guest H₂O. By virtue of this reversible thermochromic switching, this halide can be used to detect the trace amount of water in various organic solvents and humidity of moist air. In addition, such switchable dual emission further realizes application in anti-counterfeiting and information encryption-decryption. This work deepens the understanding of structure-property relationships and expands the application range of 0D metal halides.

具有多功能特性的激发响应发光开关材料对于先进的光子应用至关重要，但在卤化物钙钛矿中实现这种功能仍然是一个重大挑战。在这项工作中，我们探索了一种新的水刺激响应零维（0D） sb基卤化物[PhPz]2SbCl7·2H2O (PhPz = phenylpiperazine)，它由分离的[SbCl6]3 -八面体在[PhPz]2+阳离子基质中与客体水分子组成。在紫外激发下，[PhPz]2SbCl7·2H2O发出强烈的宽带红光，最大发射波长为645 nm，结合光学表征和理论计算证实了这种发光来自自困激子（STEs）。有趣的是，在加热-冷却循环过程中，自由水分子可以可逆地离开和进入晶格，并伴有脱水相的形成，在580 nm处表现出强烈的黄色发光，最大峰值为580nm。因此，通过对客体水的可控去除和吸附过程，实现了红光和黄色发光的可逆切换。由于这种可逆的热致变色开关，该卤化物可用于检测各种有机溶剂中的微量水和潮湿空气的湿度。此外，这种可切换的双发射进一步实现了在防伪和信息加解密方面的应用。这项工作加深了对0D金属卤化物的结构-性能关系的认识，扩大了0D金属卤化物的应用范围。

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引用次数: 0

Chromogenic and fluorogenic Schiff base sensors 显色和荧光希夫碱传感器

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-10-01 DOI: 10.1016/j.cjsc.2025.100751

Fozia Nazir , Syeda Sundas Musawar , Ashfaq Ahmad Khan , Bilal Akram , Farid Ahmed

Since their discovery by Hugo Schiff in 1864, Schiff bases and their metal complexes have gained recognition for their catalytic and biological properties. These compounds exhibit diverse functionalities, serving as catalysts in synthetic processes and displaying notable biological activities such as antifungal, antibacterial, anti-malarial, and antiviral effects. In various applications, Schiff bases serve as versatile tools, particularly in sensing applications. Through coordination with various metal ions, they form stable complexes. They are utilized as fluorescent turn-on/turn-off sensors for detecting a wide range of analytes. The coordination ability makes them valuable as chemosensor for detecting environmentally and biologically important analytes. This review provides a thorough overview of Schiff base chemosensors designed for the detection of environmental and biological significance including metal cations, anions, and neutral analytes. It is structured into four focused sections. The first section addresses the use of Schiff base chemosensor for the selective detection of various metal cations, including Ca²⁺, Al³⁺, Cr³⁺, Mn²⁺, Fe³⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺; The second section examines the application of fluorescent Schiff base sensors in detecting diverse anions such as F⁻, CN⁻, I⁻, and HSO₄⁻; The third section investigates the use of Schiff base fluorescent probes for accurate pH detection and determination; and the fourth section explores the utilization of Schiff base sensors for detecting environmentally and biologically important neutral analytes, including insecticides, pesticides, and others. Additionally, the Schiff base chemosensors for metal cations and anions section are concluded with a table, summarizing the reviewed fluorescent Schiff base sensors for enhanced clarity.

自1864年雨果·希夫（Hugo Schiff）发现希夫碱及其金属配合物以来，希夫碱及其金属配合物的催化和生物学特性得到了广泛的认可。这些化合物具有多种功能，可作为合成过程的催化剂，并具有显著的生物活性，如抗真菌、抗菌、抗疟疾和抗病毒作用。在各种应用中，希夫碱基作为多功能工具，特别是在传感应用中。通过与各种金属离子配合，形成稳定的配合物。它们被用作荧光开/关传感器，用于检测各种分析物。这种配位能力使它们成为有价值的化学传感器，用于检测环境和生物学上重要的分析物。本文综述了用于检测环境和生物意义的希夫碱化学传感器，包括金属阳离子、阴离子和中性分析物。它分为四个重点部分。第一部分介绍了使用希夫碱化学传感器选择性检测各种金属阳离子，包括Ca2+、Al3+、Cr3+、Mn2+、Fe3+、Ni2+、Cu2+、Zn2+、Cd2+、Hg2+和Pb2+；第二部分探讨了荧光希夫碱传感器在检测各种阴离子（如F−，CN−，I−和HSO4−）中的应用；第三部分探讨了使用希夫碱荧光探针进行准确的pH检测和测定；第四部分探讨了利用希夫碱传感器检测环境和生物重要的中性分析物，包括杀虫剂、农药等。此外，希夫碱化学传感器的金属阳离子和阴离子部分总结了一个表，总结了审查的荧光希夫碱传感器，以提高清晰度。

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引用次数: 0

Addressing agricultural (micro)plastics pollution: The promises and perspectives of framework-based photocatalysis 解决农业（微）塑料污染：基于框架的光催化的前景和前景

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-10-02 DOI: 10.1016/j.cjsc.2025.100752

Shuyu Li , Ning Gong , Zhi-Hao Lin , Jing Chen , Ge Chen , Jun Lv , Guangyang Liu , Yi Niu , Liao-Yuan Yao , Donghui Xu , Lin Qin

Plastics, renowned for their flexibility, stability, and cost-effectiveness, have become indispensable materials in modern life. However, their extensive use has led to a global environmental and health crisis. Especially, plastic products infiltrate agroecosystems through atmospheric deposition, irrigation water, soil contamination, and the degradation of plastic mulch films, posing significant risks to vegetable quality and safety. Traditional disposal methods, such as incineration and landfilling, are energy-intensive and ecologically harmful, necessitating the development and application of innovative technologies for plastic removal. This paper reviews representative advanced (micro)plastic removal technologies, with a particular focus on frameworks-containing photocatalysis as a promising green method for processing (micro)plastics. First, we analyze and compare traditional, then discuss emerging removal technologies. Next, we elaborate on the principles of photocatalytic degradation of plastic products, discuss key influencing factors, and classify various photocatalysts. Additionally, we highlight the limitations of conventional photocatalysts, such as TiO₂ and ZnO, and emphasize the advantages of framework materials (e.g., MOFs, COFs, ZIFs) in photocatalytic degradation, including their structural tunability and development potential. Finally, based on the current progress and applications of framework photocatalysts, we identify existing limitations and propose future research directions. This review provides a theoretical foundation and innovative technological insights to address the global challenge of plastic pollution.

塑料以其柔韧性、稳定性和性价比而闻名，已成为现代生活中不可或缺的材料。然而，它们的广泛使用导致了全球环境和健康危机。特别是，塑料制品通过大气沉降、灌溉水、土壤污染、地膜降解等途径渗入农业生态系统，对蔬菜质量安全构成重大威胁。传统的处理方法，如焚烧和堆填，是能源密集和生态有害的，需要开发和应用创新的技术来清除塑料。本文综述了具有代表性的先进（微）塑料去除技术，重点介绍了含框架光催化作为处理（微）塑料的一种有前途的绿色方法。首先，我们分析和比较了传统的去除技术，然后讨论了新兴的去除技术。接下来，我们阐述了光催化降解塑料制品的原理，讨论了关键的影响因素，并对各种光催化剂进行了分类。此外，我们强调了传统光催化剂（如TiO2和ZnO）的局限性，并强调了框架材料（如mof， COFs, zif）在光催化降解中的优势，包括它们的结构可调性和发展潜力。最后，根据目前框架光催化剂的研究进展和应用情况，指出了存在的局限性，并提出了未来的研究方向。这一综述为解决塑料污染的全球性挑战提供了理论基础和创新的技术见解。

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引用次数: 0

Binder-free bimetallic vanadium-nickel-boride-phosphide spherical structure for highly efficient and stable industrial-level water splitting 无粘结剂双金属钒镍硼化磷化物球形结构，用于高效稳定的工业级水分解

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-09-26 DOI: 10.1016/j.cjsc.2025.100747

Sumiya Akter Dristy , Md Ahasan Habib , Mehedi Hasan Joni, Md Najibullah, Rutuja Mandavkar, Shusen Lin, Jihoon Lee

The development of robust, cost-effective and high-performance electrocatalysts is essential for industrial-scale green hydrogen production under high-current operating conditions (> 500 mA/cm²) to ensure both high output and economic efficiency. Herein, a binder-free bimetallic vanadium-nickel-boride-phosphide (VNiBP) spherical electrocatalyst (SE) is synthesized via a simple hydrothermal method, followed by post-annealing. The VNiBP catalyst exhibits low overpotentials of 91 mV for the hydrogen evolution reaction (HER) and 270 mV for the oxygen evolution reaction (OER) at 100 mA/cm² in 1 M KOH with stable operation over 150 h, surpassing most of the state-of-the-art electrocatalysts. The bifunctional VNiBP (–, +) exhibits a low turnover voltage of 1.57 V at 100 mA/cm² and outperforms the Pt/C||RuO₂ benchmark system up to 2000 mA/cm² high-current density. The Pt/C||VNiBP hybrid configuration shows a low 2-E cell voltage of 2.55 V at 2000 mA/cm² under industrially relevant conditions (6 M KOH, 60 °C). Notably, the VNiBP demonstrates exceptional long-term stability, maintaining continuous operation for over 6 days in both 1 M and 6 M KOH at 1000 mA/cm². The outstanding overall water splitting (OWS) performance can be attributed to the synergistic combination of rapid intermediate formation, optimized adsorption/desorption kinetics, high electrochemical surface area and low charge transfer resistance offered by favorable composition and spherical morphology.

在高电流操作条件下（500毫安/平方厘米）实现工业规模的绿色制氢，确保高产出和经济效益，开发强大、经济高效的电催化剂至关重要。本文采用简单的水热法合成了无粘结剂的双金属钒镍硼化磷化物（VNiBP）球形电催化剂（SE），并进行了后退火。VNiBP催化剂在1 M KOH条件下，在100 mA/cm2条件下，析氢反应（HER）的过电位为91 mV，析氧反应（OER）的过电位为270 mV，稳定运行150 h以上，超过了大多数最先进的电催化剂。双功能VNiBP（-, +）在100 mA/cm2时具有1.57 V的低转换电压，并且在高达2000 mA/cm2的高电流密度下优于Pt/C||RuO2基准系统。Pt/C||VNiBP混合结构在工业相关条件下（6 M KOH, 60°C），在2000 mA/cm2下具有2.55 V的低2-E电池电压。值得注意的是，VNiBP表现出优异的长期稳定性，在1 M和6 M KOH下，在1000 mA/cm2下连续运行超过6天。优异的整体水分解（OWS）性能可归因于快速中间体形成、优化的吸附/解吸动力学、良好的组成和球形形貌提供的高电化学表面积和低电荷转移阻力的协同组合。

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引用次数: 0

Fluorescence enhancement of perylene diimide: Design strategy and application 苝二亚胺的荧光增强：设计策略及应用

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-10-04 DOI: 10.1016/j.cjsc.2025.100756

Ya-Ru Qu , Kai-Li Tian , Han-Jun Huang , Jia-Jun Tu , Ai-Hao Chen , Hai-Jun Sun , Maxim V. Bermeshev , Shao-Jie Wang , Wen-Bin Li , Xiang-Kui Ren

Perylene diimide (PDI) derivatives have emerged as a class of important organic fluorescent materials owing to their high extinction coefficient, excellent thermal and photostability, and versatile structural tunability. However, due to its intrinsic rigid planar structure, π-π stacking is easy to occur, resulting in aggregation-caused quenching (ACQ). In recent years, extensive efforts have been devoted to overcome this challenge and enhance the fluorescence performance of PDIs. This review systematically summarizes representative strategies from three major perspectives: (i) Rational molecular design, including the introduction of bulky aromatic substituents, dendritic or polyhedral oligomeric silsesquioxane (POSS) units to provide steric hindrance, as well as the activation of aggregation-induced emission (AIE); (ii) Polymer-based regulation strategies, including physical blending with polymer hosts and covalent integration into polymer backbones, which provide spatial isolation and structural robustness; and (iii) Supramolecular assembly, where host-guest inclusion and self-assembly pathways precisely tune intermolecular packing and excitonic coupling. These strategies have enabled significant improvements in fluorescence quantum yield (FLQY) across solution, aggregate, and solid states. Furthermore, highly emissive perylene diimide (PDI) derivatives have demonstrated broad applicability in biomedicine, sensing and anti-counterfeiting, and optoelectronic devices such as organic light-emitting diodes (OLEDs). This review highlights the fundamental design principles, performance optimization strategies, and emerging application frontiers of PDI-based luminescent materials, providing guidance for their further development toward multifunctional and sustainable optoelectronic technologies.

苝酰二亚胺（PDI）衍生物因其高消光系数、优异的热稳定性和光稳定性以及多种结构可调性而成为一类重要的有机荧光材料。然而，由于其固有的刚性平面结构，π-π堆积容易发生，导致聚集引起的猝灭（ACQ）。近年来，人们一直在努力克服这一挑战，提高pdi的荧光性能。本文从三个主要方面系统总结了具有代表性的策略：(1)合理的分子设计，包括引入大体积芳香取代基、树突或多面体低聚硅氧烷（POSS）单元来提供空间位阻，以及激活聚集诱导发射（AIE）；㈡基于聚合物的调节策略，包括与聚合物宿主的物理共混和共价整合到聚合物骨架中，从而提供空间隔离和结构坚固性；（iii）超分子组装，其中主-客体包涵和自组装途径精确调节分子间包装和激子耦合。这些策略使荧光量子产率（FLQY）在溶液、聚集体和固体状态有了显著的提高。此外，高发射度的苝二亚胺（PDI）衍生物在生物医学、传感和防伪以及光电器件（如有机发光二极管（oled））中已被证明具有广泛的适用性。本文综述了pdi基发光材料的基本设计原理、性能优化策略和新兴应用领域，为pdi基发光材料向多功能和可持续光电技术的进一步发展提供了指导。

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引用次数: 0

A stereochemically stable double-helical trinuclear bis(tridipyrrin) complex exhibiting near-infrared chiroptical properties 一种立体化学稳定的双螺旋三核二（三吡啶）配合物，具有近红外热学性质

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-09-16 DOI: 10.1016/j.cjsc.2025.100722

Yingjian Shang , Xuefeng Zhao , Tao Wu , Yanhui He , Xing Guo , Hongwei Si , Lijuan Jiao , Erhong Hao , Wei Miao

A novel double-stranded trinuclear bis(tridipyrrin) zinc(II) complex, constructed from a linear π-conjugated tridipyrrin ligand, was synthesized and characterized. The complex featuring six directly linked dipyrrin units exhibits a stable double-helical structure with two non-superimposable P and M enantiomers, as confirmed by X-ray crystallography. Chirality was further demonstrated through HPLC separation and mirror-image circular dichroism (CD) spectra. The complex shows strong near-infrared (NIR) absorption and excellent solubility in various solvents, attributed to its sterically hindered structure. Spectroscopic, electrochemical, and theoretical studies revealed its unique electronic properties and redox behavior. This work advances the design of chiral NIR-active metallo-supramolecular systems and highlights potential applications in chiroptical materials.

合成了一种新型的双链三核双（三吡啶）锌（II）配合物，该配合物是由线性π共轭三吡啶配体构成的。x射线晶体学证实，该配合物具有六个直接相连的二吡啶单元，具有两个不重叠的P和M对映体，具有稳定的双螺旋结构。通过HPLC分离和镜像圆二色光谱进一步证实了手性。由于其位阻结构，该配合物在各种溶剂中具有较强的近红外吸收和良好的溶解度。光谱、电化学和理论研究揭示了其独特的电子性质和氧化还原行为。这项工作推进了手性nir活性金属超分子体系的设计，并强调了手性nir活性金属超分子体系在手性材料中的潜在应用。

引用次数: 0

Solvent-coordination directed control of electron transfer dynamics in photoactive complexes 光活性配合物中电子转移动力学的溶剂配位定向控制

IF 10.3 4区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

结构化学

Pub Date : 2025-12-01 Epub Date: 2025-10-07 DOI: 10.1016/j.cjsc.2025.100753

Yan-Rui Zhao, Jin Zhang, Shi-Kun Yan, Guang-Zhi Zhou, Ya-Hui Wang, Qi-Yue Xin, Ji-Xiang Hu

Photochromic materials attract significant attention for their applications in anticounterfeiting devices, optical switches and molecular sensors. However, the influence of solvent molecules, particularly coordinated solvents, on electron transfer (ET) photochromic systems remains poorly understood. In this study, we synthesized a series of isostructural metal-organic complexes (MOCs), [Mn(ADC)(L)]_n (ADC = 9,10-anthracenedicarboxylic acid, L = DMF for 1, DMA for 2, MEA for 3, and DMSO for 4) to investigate the solvent-chromic behavior. All these MOCs exhibit typical radical-induced chromism upon illumination with a xenon lamp at room temperature. It is worth noting that coordination solvent molecules significantly modulate the photochromic response rate. Among the compounds studied, compound 1 exhibits the fastest response, while compound 3 shows the slowest. This variation in rate correlates with differences in the optimal ET path length within their structures. Specifically, solvent molecules regulate the C–H···π interaction distance through their steric hindrance and electronic properties. Shorter C–H···π paths facilitate more efficient ET upon photoexcitation, thus leading to faster photochromic response rates. Furthermore, illumination actuates magnetic couplings between photogenerated radicals and Mn²⁺ centers, resulting in a significant increase in room-temperature magnetization, demonstrating a photomagnetic response. This study demonstrates that coordinating solvent selection effectively controls photoinduced ET behavior, providing new insights for designing advanced photoactive materials.

光致变色材料在防伪器件、光开关和分子传感器等方面的应用备受关注。然而，溶剂分子，特别是配位溶剂，对电子转移（ET）光致变色系统的影响仍然知之甚少。在本研究中，我们合成了一系列同结构金属-有机配合物（MOCs）， [Mn(ADC)(L)]n （ADC = 9,10-蒽二羧酸，L = DMF为1，DMA为2，MEA为3，DMSO为4）来研究其溶剂-变色行为。这些MOCs在室温氙灯照射下均表现出典型的自由基致变色现象。值得注意的是，配位溶剂分子显著调节光致变色反应速率。在所研究的化合物中，化合物1的反应最快，而化合物3的反应最慢。这种速率的变化与它们结构内最佳ET路径长度的差异有关。溶剂分子通过空间位阻和电子性质调节C-H··π相互作用距离。更短的C-H··π路径有助于光激发时更有效的ET，从而导致更快的光致变色响应速率。此外，光照激发了光生成自由基和Mn2+中心之间的磁耦合，导致室温磁化强度显著增加，显示出光磁响应。本研究表明，协调溶剂选择有效地控制了光致ET行为，为设计先进的光活性材料提供了新的见解。

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