Login In
2025 Volume 44 Issue 12
2025, 44(12): 100718
doi: 10.1016/j.cjsc.2025.100718
Abstract:
2025, 44(12): 100720
doi: 10.1016/j.cjsc.2025.100720
Abstract:
2025, 44(12): 100721
doi: 10.1016/j.cjsc.2025.100721
Abstract:
2025, 44(12): 100722
doi: 10.1016/j.cjsc.2025.100722
Abstract:
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.
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.
2025, 44(12): 100729
doi: 10.1016/j.cjsc.2025.100729
Abstract:
The quantitative detection of biological metabolites is a crucial route for early diagnosis of human diseases. Exhaled ammonia (NH3), originating from abnormal metabolism, is normally recognized as the biomarker for liver and kidney lesions. Therefore, developing highly sensitive fluorescent sensing materials is expected to replace the traditional clinical blood tests and facilitate painless diagnosis and telemedicine for patients. However, the weak interaction for ammonia and the small color switching range of fluorescence sensors become the most pressing problem at present. Herein, a porphyrin-based hydrogen-bonded organic framework (HOF-6) with abundant supermolecule interactions in the confined pore space is developed for highly sensitive ammonia detection. The strong interactions between ammonia and the framework greatly promote the electron rearrangement and enhance the intensity of fluorescence, enabling HOF-6 to successfully achieve trace amounts of ammonia sensing with the limit detection of 0.2 ppm. With the ultrahigh selectivity for ammonia, HOF-6 can accurately determine the amount of ammonia in breath of patients, and the test results are highly consistent with blood ammonia levels. The tailor-made multiple interactions in the confined pore space provide an effective approach for highly sensitive ammonia detection, as well as brings good news to liver and kidney patients for non-invasive diagnosis and real-time health monitoring.
The quantitative detection of biological metabolites is a crucial route for early diagnosis of human diseases. Exhaled ammonia (NH3), originating from abnormal metabolism, is normally recognized as the biomarker for liver and kidney lesions. Therefore, developing highly sensitive fluorescent sensing materials is expected to replace the traditional clinical blood tests and facilitate painless diagnosis and telemedicine for patients. However, the weak interaction for ammonia and the small color switching range of fluorescence sensors become the most pressing problem at present. Herein, a porphyrin-based hydrogen-bonded organic framework (HOF-6) with abundant supermolecule interactions in the confined pore space is developed for highly sensitive ammonia detection. The strong interactions between ammonia and the framework greatly promote the electron rearrangement and enhance the intensity of fluorescence, enabling HOF-6 to successfully achieve trace amounts of ammonia sensing with the limit detection of 0.2 ppm. With the ultrahigh selectivity for ammonia, HOF-6 can accurately determine the amount of ammonia in breath of patients, and the test results are highly consistent with blood ammonia levels. The tailor-made multiple interactions in the confined pore space provide an effective approach for highly sensitive ammonia detection, as well as brings good news to liver and kidney patients for non-invasive diagnosis and real-time health monitoring.
2025, 44(12): 100734
doi: 10.1016/j.cjsc.2025.100734
Abstract:
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.
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.
2025, 44(12): 100744
doi: 10.1016/j.cjsc.2025.100744
Abstract:
Separation of ternary C4 olefins (n-butene, iso-butene and 1,3-butadiene) is very challenging but crucial in the petrol-chemical industry due to their similar molecular sizes and properties. Herein, to optimize the separation efficiency for separation of C4 olefins, a new Hofmann-type MOF, [Ni(piz)Ni(CN)4] (piz = piperazine)—isostructural to the typical one [Ni(pyz)Ni(CN)4] (pyz = pyrazine), has been synthesized by a facile method from aqueous solution. The pore size reduction of [Ni(piz)Ni(CN)4] (3.62 Å, in contrast to 3.85 Å in [Ni(pyz)Ni(CN)4]) results in negligible iso-butene (i-C4H8) uptake (from 2.92 to 0.04 mmol g−1) whereas retaining significant uptake for 1,3-butadiene (1,3-C4H6, 1.96 mmol g−1) and n-butene (n-C4H8, 1.47 mmol g−1), showing much higher uptake ratios of 1,3-C4H6/i-C4H8 (47) and n-C4H8/i-C4H8 (35) that outperform most of the benchmark porous materials for separating C4 olefins. Breakthrough experiments demonstrate successful separation of high-purity (99.9999%) i-C4H8 and 1,3-C4H6 from equimolar 1,3-C4H6/i-C4H8, n-C4H8/i-C4H8 and 1,3-C4H6/n-C4H8/i-C4H8 mixtures.
Separation of ternary C4 olefins (n-butene, iso-butene and 1,3-butadiene) is very challenging but crucial in the petrol-chemical industry due to their similar molecular sizes and properties. Herein, to optimize the separation efficiency for separation of C4 olefins, a new Hofmann-type MOF, [Ni(piz)Ni(CN)4] (piz = piperazine)—isostructural to the typical one [Ni(pyz)Ni(CN)4] (pyz = pyrazine), has been synthesized by a facile method from aqueous solution. The pore size reduction of [Ni(piz)Ni(CN)4] (3.62 Å, in contrast to 3.85 Å in [Ni(pyz)Ni(CN)4]) results in negligible iso-butene (i-C4H8) uptake (from 2.92 to 0.04 mmol g−1) whereas retaining significant uptake for 1,3-butadiene (1,3-C4H6, 1.96 mmol g−1) and n-butene (n-C4H8, 1.47 mmol g−1), showing much higher uptake ratios of 1,3-C4H6/i-C4H8 (47) and n-C4H8/i-C4H8 (35) that outperform most of the benchmark porous materials for separating C4 olefins. Breakthrough experiments demonstrate successful separation of high-purity (99.9999%) i-C4H8 and 1,3-C4H6 from equimolar 1,3-C4H6/i-C4H8, n-C4H8/i-C4H8 and 1,3-C4H6/n-C4H8/i-C4H8 mixtures.
High-entropy PdPtRhFeCuMo metallene nanoribbons for electro-reforming PET plastic into glycolic acid
2025, 44(12): 100745
doi: 10.1016/j.cjsc.2025.100745
Abstract:
The electrochemical upgrading of polyethylene terephthalate (PET) plastics represents a highly promising strategy for achieving high-value utilization of waste resources, and its efficiency is highly related to identify active electrocatalysts for PET-derived ethylene glycol oxidation reaction (EGOR). In this work, atomically thin high-entropy PdPtRhFeCuMo metallene nanoribbons (PdPtRhFeCuMo HMRs) have been synthesized and served as high-performance catalysts for electro-reforming PET plastic, which possess a high current density of 180 mA cm−2 at a low potential of 0.9 V for EGOR, with excellent Faraday efficiency (FE) of 96.81% for highly efficient and selective conversion of EG into high-value-added glycolic acid (GA). Experimental and theoretical results reveal that the multi-metallic synergistic effect of PdPtRhFeCuMo HMRs effectively modulates adsorption behavior of intermediates and reduce the EGOR energy barrier, thus promoting the selective EG-to-GA conversion. This study proposes the reasonable design of high-entropy metallene nanoribbons for the electrochemical upgrading of PET plastics to high-value C2 products.
The electrochemical upgrading of polyethylene terephthalate (PET) plastics represents a highly promising strategy for achieving high-value utilization of waste resources, and its efficiency is highly related to identify active electrocatalysts for PET-derived ethylene glycol oxidation reaction (EGOR). In this work, atomically thin high-entropy PdPtRhFeCuMo metallene nanoribbons (PdPtRhFeCuMo HMRs) have been synthesized and served as high-performance catalysts for electro-reforming PET plastic, which possess a high current density of 180 mA cm−2 at a low potential of 0.9 V for EGOR, with excellent Faraday efficiency (FE) of 96.81% for highly efficient and selective conversion of EG into high-value-added glycolic acid (GA). Experimental and theoretical results reveal that the multi-metallic synergistic effect of PdPtRhFeCuMo HMRs effectively modulates adsorption behavior of intermediates and reduce the EGOR energy barrier, thus promoting the selective EG-to-GA conversion. This study proposes the reasonable design of high-entropy metallene nanoribbons for the electrochemical upgrading of PET plastics to high-value C2 products.
2025, 44(12): 100747
doi: 10.1016/j.cjsc.2025.100747
Abstract:
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.
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.
2025, 44(12): 100749
doi: 10.1016/j.cjsc.2025.100749
Abstract:
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.
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.
2025, 44(12): 100751
doi: 10.1016/j.cjsc.2025.100751
Abstract:
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.
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.
2025, 44(12): 100752
doi: 10.1016/j.cjsc.2025.100752
Abstract:
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.
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.
2025, 44(12): 100753
doi: 10.1016/j.cjsc.2025.100753
Abstract:
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.
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.
2025, 44(12): 100756
doi: 10.1016/j.cjsc.2025.100756
Abstract:
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.
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.
2025, 44(12): 100757
doi: 10.1016/j.cjsc.2025.100757
Abstract:
Diamond-like AgGaS2 (DL AGS), as the typical infrared nonlinear optical (IR NLO) material, has suffered from its intrinsic drawbacks like narrow band gap (Eg) and low laser-induced damage threshold (LIDT). In this work, by first introducing [NaS8] polyhedral unit into the A2IQVI-Ag2QVI-C2IIIQ3VI system, a new Ag-based sulfide NaAg3Ga8S14 with diamond-like framework (DLF) has been successfully synthesized via a high-temperature solid-state method in experiment. The compound shows a wide Eg (∼3.0 eV), high LIDT (3.0 × AGS) and moderate phase-matching NLO response (∼0.7 × AGS), effectively balancing the Eg (≥ 3.0 eV) and NLO response (≥ 0.5 × AGS), demonstrating its promise for IR NLO applications. Theoretical calculations elucidate the orbital hybridization between Na 3s, Ag 4d5s and S 3p enhances Eg, and the aligned NLO-active units ([AgS4] and [GaS4]) induce moderate NLO response in the compound. These findings not only expand the chemical and structural diversities of Ag-based chalcogenides, but also provide effective strategies for designing DLF functional materials derived from diamond-like structures.
Diamond-like AgGaS2 (DL AGS), as the typical infrared nonlinear optical (IR NLO) material, has suffered from its intrinsic drawbacks like narrow band gap (Eg) and low laser-induced damage threshold (LIDT). In this work, by first introducing [NaS8] polyhedral unit into the A2IQVI-Ag2QVI-C2IIIQ3VI system, a new Ag-based sulfide NaAg3Ga8S14 with diamond-like framework (DLF) has been successfully synthesized via a high-temperature solid-state method in experiment. The compound shows a wide Eg (∼3.0 eV), high LIDT (3.0 × AGS) and moderate phase-matching NLO response (∼0.7 × AGS), effectively balancing the Eg (≥ 3.0 eV) and NLO response (≥ 0.5 × AGS), demonstrating its promise for IR NLO applications. Theoretical calculations elucidate the orbital hybridization between Na 3s, Ag 4d5s and S 3p enhances Eg, and the aligned NLO-active units ([AgS4] and [GaS4]) induce moderate NLO response in the compound. These findings not only expand the chemical and structural diversities of Ag-based chalcogenides, but also provide effective strategies for designing DLF functional materials derived from diamond-like structures.
2025, 44(12): 100758
doi: 10.1016/j.cjsc.2025.100758
Abstract:
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.
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.
2025, 44(12): 100759
doi: 10.1016/j.cjsc.2025.100759
Abstract:
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 were found to be exquisitely adjusted by the distinct coordination environments of Sn4+ centers. Notably, Sn2EuL2-R/S demonstrates CPL activity in both the near-UV (|glum| = 1.7 × 10-3) and visible (|glum| = 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.
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 were found to be exquisitely adjusted by the distinct coordination environments of Sn4+ centers. Notably, Sn2EuL2-R/S demonstrates CPL activity in both the near-UV (|glum| = 1.7 × 10-3) and visible (|glum| = 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.
