Fengqi Zhang, Yongsheng Yang, Tingting Lu, Ke Hu, Zhen Zhao
Stimuli-responsive luminescent materials can respond to external stimuli, exhibiting dynamic changes in their luminescent properties, and thus show broad application prospects in various fields such as optical sensing, security anti-counterfeiting, and information storage. The reversible recovery capability of luminescent response performance and the ease of implementation of recovery conditions are the core indicators for evaluating its practical application value. Herein, a complex (Cd2(9-AC)4(IM)2, 9-HAC for anthracene-9-carboxylic acid and IM for imidazole) system based on exciplex luminescence have been constructed. By disrupting the interactions between donor (9-HAC) and acceptor (IM) molecules through force-induced action or acid-induced action, mechanochromic luminescence (MCL) and acidochromic luminescence (ACL) properties are achieved. All these stimulus-induced luminescent changes can be reversibly restored through conventional solvent or alkali vapor fumigation. Notably, MCL performance can also be restored via ultraviolet irradiation, which is more cost-effective, convenient and environmentally friendly. This process is achieved through the repair of charge transfer pathways between donor and acceptor molecules by photogenerated free radicals. Leveraging the reversible MCL and photo-recoverable luminescence of this complex, we have ultimately designed a reusable paper capable of ink-free writing and solvent-free erasing, opening an entirely new path for promoting environmentally friendly and sustainable paper applications.
{"title":"Exciplex-based multi-stimuli-responsive luminescent materials: photo-recoverable mechanochromic luminescence for reusable paper applications","authors":"Fengqi Zhang, Yongsheng Yang, Tingting Lu, Ke Hu, Zhen Zhao","doi":"10.1039/d5qi02419f","DOIUrl":"https://doi.org/10.1039/d5qi02419f","url":null,"abstract":"Stimuli-responsive luminescent materials can respond to external stimuli, exhibiting dynamic changes in their luminescent properties, and thus show broad application prospects in various fields such as optical sensing, security anti-counterfeiting, and information storage. The reversible recovery capability of luminescent response performance and the ease of implementation of recovery conditions are the core indicators for evaluating its practical application value. Herein, a complex (Cd2(9-AC)4(IM)2, 9-HAC for anthracene-9-carboxylic acid and IM for imidazole) system based on exciplex luminescence have been constructed. By disrupting the interactions between donor (9-HAC) and acceptor (IM) molecules through force-induced action or acid-induced action, mechanochromic luminescence (MCL) and acidochromic luminescence (ACL) properties are achieved. All these stimulus-induced luminescent changes can be reversibly restored through conventional solvent or alkali vapor fumigation. Notably, MCL performance can also be restored via ultraviolet irradiation, which is more cost-effective, convenient and environmentally friendly. This process is achieved through the repair of charge transfer pathways between donor and acceptor molecules by photogenerated free radicals. Leveraging the reversible MCL and photo-recoverable luminescence of this complex, we have ultimately designed a reusable paper capable of ink-free writing and solvent-free erasing, opening an entirely new path for promoting environmentally friendly and sustainable paper applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"144 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145949903","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}
Self-reduction phenomena are commonly observed during the synthesis of fluorescent materials, but precise control over the self-reduction behavior of such materials remains challenging. In this study, we effectively suppressed the self-reduction behavior of BaMg 1.072 Al 9.928 O 17 : Mn (BMAO: Mn) materials through co-doping with Li + ions. As the concentration of Li ions increases, the self-reduction behavior of the material is inhibited to varying degrees. The underlying mechanisms responsible for the suppression of self-reduction are investigated in detail and multi-color emission based on varying Li + ions concentration. The research demonstrates that Li + ions effectively suppresses the self-reduction behavior of Mn through occupying interstitial sites or substituting tetrahedral Mg 2+ sites in the BMAO lattice, thereby regulating the Mn valence state. Finally, thanks to the distinct thermally quenched behaviors of Mn 2+ and Mn 4+ as well as temperature-dependent multi-color luminescence, a multi-modal temperature sensor and optical information encryption are achieved.
自还原现象在荧光材料的合成过程中很常见，但对这种材料的自还原行为的精确控制仍然具有挑战性。在本研究中，我们通过Li +离子的共掺杂，有效抑制了BaMg 1.072 Al 9.928 O 17: Mn （BMAO: Mn）材料的自还原行为。随着锂离子浓度的增加，材料的自还原行为受到不同程度的抑制。详细研究了抑制自还原的潜在机制，并根据不同的Li +离子浓度研究了多色发射。研究表明，Li +离子通过占据BMAO晶格中的间隙位或取代四面体Mg 2+位，有效抑制Mn的自还原行为，从而调控Mn的价态。最后，利用mn2 +和mn4 +不同的热猝灭行为以及与温度相关的多色发光特性，实现了多模态温度传感器和光信息加密。
{"title":"Mn Valence Transition via Li + Structure Modulation and Charge Transfer for Multi-modal Temperature Sensor and Optical Encryption","authors":"Heng Dai, Zhichao Liu, Xinran Wang, Junli Liu, Anxi Zhu, Xiuxia Yang","doi":"10.1039/d5qi02116b","DOIUrl":"https://doi.org/10.1039/d5qi02116b","url":null,"abstract":"Self-reduction phenomena are commonly observed during the synthesis of fluorescent materials, but precise control over the self-reduction behavior of such materials remains challenging. In this study, we effectively suppressed the self-reduction behavior of BaMg <small><sub>1.072</sub></small> Al <small><sub>9.928</sub></small> O <small><sub>17</sub></small> : Mn (BMAO: Mn) materials through co-doping with Li <small><sup>+</sup></small> ions. As the concentration of Li ions increases, the self-reduction behavior of the material is inhibited to varying degrees. The underlying mechanisms responsible for the suppression of self-reduction are investigated in detail and multi-color emission based on varying Li <small><sup>+</sup></small> ions concentration. The research demonstrates that Li <small><sup>+</sup></small> ions effectively suppresses the self-reduction behavior of Mn through occupying interstitial sites or substituting tetrahedral Mg <small><sup>2+</sup></small> sites in the BMAO lattice, thereby regulating the Mn valence state. Finally, thanks to the distinct thermally quenched behaviors of Mn <small><sup>2+</sup></small> and Mn <small><sup>4+</sup></small> as well as temperature-dependent multi-color luminescence, a multi-modal temperature sensor and optical information encryption are achieved.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"433-435 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145962199","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}
The exhaustive hydrodehalogenation (HDH) of CF3 groups in pyridines and of C(sp2)-X (X = F, Cl, Br, I) bonds in pyridines and arenes was catalyzed by [Ni(COD)2] employing NH3BH3 in the presence of KOtBu at room temperature. The system showed a broad substrate scope, including OMe and NH2 substituted pyridines, and enabled the C(sp2)-X HDH of several environmental pollutants and the DDF of CF3 groups and C(sp2)-X bonds in pyridines, affording CD3-substituted pyridines with d incorporation at the CD3 group in >99% and high degrees of d incorporation at the ring. Mechanistic studies for the HDF of 2-trifluoromethylpyridine allowed to identify three simultaneous HDF cycles operative with the first cycle being the rate-determining and the reaction of the [Ni(COD)2] precatalyst with the H source being the entry pathway to the cycle. The key behind catalyst efficiency for exhaustive HDH and its broad substrate scope has been traced back to the use of KOtBu which enabled hydride transfer from NH3BH3 to the [Ni(COD)2] precatalyst, rendering access to a nickelate(0) hydride complex responsible for C-F activation. Competition experiments employing pyridines allowed to rationalize the catalyst selectivity for different types of C(sp2)-X bonds, for C(sp2)-F vs. C(sp3)-F bonds as well as the impact of the position of CF3 groups on catalyst efficiency.
{"title":"Bis(Cyclooctadiene)Nickel(0)-Catalyzed Exhaustive C(sp2)-X and C(sp3)-F Hydrodehalogenation and Deuterodefluorination of Pyridines and Arenes with Broad Substrate Scope","authors":"Himani Ahuja, Rebeca Arevalo","doi":"10.1039/d6qi00010j","DOIUrl":"https://doi.org/10.1039/d6qi00010j","url":null,"abstract":"The exhaustive hydrodehalogenation (HDH) of CF3 groups in pyridines and of C(sp2)-X (X = F, Cl, Br, I) bonds in pyridines and arenes was catalyzed by [Ni(COD)2] employing NH3BH3 in the presence of KOtBu at room temperature. The system showed a broad substrate scope, including OMe and NH2 substituted pyridines, and enabled the C(sp2)-X HDH of several environmental pollutants and the DDF of CF3 groups and C(sp2)-X bonds in pyridines, affording CD3-substituted pyridines with d incorporation at the CD3 group in >99% and high degrees of d incorporation at the ring. Mechanistic studies for the HDF of 2-trifluoromethylpyridine allowed to identify three simultaneous HDF cycles operative with the first cycle being the rate-determining and the reaction of the [Ni(COD)2] precatalyst with the H source being the entry pathway to the cycle. The key behind catalyst efficiency for exhaustive HDH and its broad substrate scope has been traced back to the use of KOtBu which enabled hydride transfer from NH3BH3 to the [Ni(COD)2] precatalyst, rendering access to a nickelate(0) hydride complex responsible for C-F activation. Competition experiments employing pyridines allowed to rationalize the catalyst selectivity for different types of C(sp2)-X bonds, for C(sp2)-F vs. C(sp3)-F bonds as well as the impact of the position of CF3 groups on catalyst efficiency.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"43 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955865","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}
Annie Regan, Vaishali Kshirsagar, Paul F. Gramelspacher, Thomas J. Boggess, Anuraj S. Kshirsagar, Charles Edwin Webster, Sidney E. Creutz
Nanocrystals of mixed metal chalcogenides such as silver bismuth sulfide (AgBiS2) offer a potential route to low-cost, environmentally friendly solar absorbers. Realizing the full potential of these materials requires a high degree of control over their properties and preparation. An understanding of the mechanisms by which molecular precursors undergo conversion and decomposition reactions during synthesis is essential for achieving this synthetic control and reproducibility. Here, we have expanded on the development of AgBiS2 nanocrystal synthesis using N,N-diethyldithiocarbamate complexes of Ag+ and Bi3+ as single-source precursors in oleylamine (OLA), establishing it as a reliable approach to high-purity and highly crystalline AgBiS2 nanomaterials. Although size tunability with this method is limited, we unexpectedly found that the addition of dodecanethiol (DDT) to the reaction mixture significantly accelerated the precursor decomposition at lower temperatures, leading to smaller size nanocrystalline domains, albeit with detrimental effects on the particle morphology. In order to understand the origin of this effect, we studied the kinetics and mechanism of precursor decomposition under different conditions using variable-temperature NMR in combination with DFT computations. We found that the use of DDT in combination with OLA promotes acid-catalyzed pathways for N,N-diethyldithiocarbamate transamidation with OLA, ultimately inducing low-temperature C-S bond cleavage. Demonstrating the advantages of this mechanistic understanding, we redesigned a new synthesis using a CS2 additive in combination with dithiocarbamate precursors which produces high-quality, quantum- confined AgBiS2 nanocrystals. In addition to new routes to size-tunable AgBiS2 nanocrystals, these studies provide potentially useful mechanistic insights about dialkyldithiocarbamate precursor conversion reactions in general, and how they can be rationally controlled.
{"title":"AgBiS2 Nanocrystal Synthesis from Molecular Precursors: Insights into the Acid-Catalyzed Decomposition of Dialkyldithiocarbamate Ligands","authors":"Annie Regan, Vaishali Kshirsagar, Paul F. Gramelspacher, Thomas J. Boggess, Anuraj S. Kshirsagar, Charles Edwin Webster, Sidney E. Creutz","doi":"10.1039/d5qi02124c","DOIUrl":"https://doi.org/10.1039/d5qi02124c","url":null,"abstract":"Nanocrystals of mixed metal chalcogenides such as silver bismuth sulfide (AgBiS<small><sub>2</sub></small>) offer a potential route to low-cost, environmentally friendly solar absorbers. Realizing the full potential of these materials requires a high degree of control over their properties and preparation. An understanding of the mechanisms by which molecular precursors undergo conversion and decomposition reactions during synthesis is essential for achieving this synthetic control and reproducibility. Here, we have expanded on the development of AgBiS<small><sub>2</sub></small> nanocrystal synthesis using N,N-diethyldithiocarbamate complexes of Ag<small><sup>+</sup></small> and Bi<small><sup>3+</sup></small> as single-source precursors in oleylamine (OLA), establishing it as a reliable approach to high-purity and highly crystalline AgBiS<small><sub>2</sub></small> nanomaterials. Although size tunability with this method is limited, we unexpectedly found that the addition of dodecanethiol (DDT) to the reaction mixture significantly accelerated the precursor decomposition at lower temperatures, leading to smaller size nanocrystalline domains, albeit with detrimental effects on the particle morphology. In order to understand the origin of this effect, we studied the kinetics and mechanism of precursor decomposition under different conditions using variable-temperature NMR in combination with DFT computations. We found that the use of DDT in combination with OLA promotes acid-catalyzed pathways for N,N-diethyldithiocarbamate transamidation with OLA, ultimately inducing low-temperature C-S bond cleavage. Demonstrating the advantages of this mechanistic understanding, we redesigned a new synthesis using a CS<small><sub>2</sub></small> additive in combination with dithiocarbamate precursors which produces high-quality, quantum- confined AgBiS<small><sub>2</sub></small> nanocrystals. In addition to new routes to size-tunable AgBiS<small><sub>2</sub></small> nanocrystals, these studies provide potentially useful mechanistic insights about dialkyldithiocarbamate precursor conversion reactions in general, and how they can be rationally controlled.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"47 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955863","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}
The growing demand for seafood safety necessitates smart sensor with real-time monitoring capability for biomarker, triethylamine (TEA). However, it still faces tremendous challenges due to limited sensitivity and selectivity of sensing material. This study develops a topological transformation from Ru-MIL-68 precursor to Ru-doped In2O3 hollow hexagonal prism. These structural merits, including hierarchical porosity, uniform Ru dispersion, and abundant oxygen vacancies, endow this material with enhanced gas adsorption-diffusion kinetics and surface reactivity. The optimized Ru-In2O3-0.8 sensor exhibits exceptional TEA sensing performance: ultrahigh response (Ra/Rg = 493 ~ 100 ppm), fast recovery (τrec = 22 s), and low detection limit (LOD = 11.3 ppb). Density functional theory calculations delineate that TEA binds preferentially to the Ru-In2O3 surface with a much larger adsorption energy than that of TEA on bare In2O3 or other gas molecules on Ru-In2O3, supporting the enhanced sensitivity and selectivity achieved by introducing Ru. Furthermore, a smart gas sensing system based on Ru-In2O3-0.8 material demonstrates real-time half-fin anchovy freshness monitoring application on mobile phone. This work not only proposes the structure modulations for exploration of advanced sensing materials, but also guides the potential for real-time analysis, monitoring and diagnosis.
{"title":"Wireless gas sensing system enabling real-time seafood freshness monitoring based on Ru-In2O3 microtubes with dual-enhanced sensitivity and selectivity","authors":"Xuezhi Song, Yuxiang Chen, Jintao Zhao, De-Kun Liu, Ziwei Lv, Yueying Wang, Zhaonan Zuo, Yulan Meng, Fei Li, Xiaofeng Wang, Zhenquan Tan","doi":"10.1039/d5qi02410b","DOIUrl":"https://doi.org/10.1039/d5qi02410b","url":null,"abstract":"The growing demand for seafood safety necessitates smart sensor with real-time monitoring capability for biomarker, triethylamine (TEA). However, it still faces tremendous challenges due to limited sensitivity and selectivity of sensing material. This study develops a topological transformation from Ru-MIL-68 precursor to Ru-doped In2O3 hollow hexagonal prism. These structural merits, including hierarchical porosity, uniform Ru dispersion, and abundant oxygen vacancies, endow this material with enhanced gas adsorption-diffusion kinetics and surface reactivity. The optimized Ru-In2O3-0.8 sensor exhibits exceptional TEA sensing performance: ultrahigh response (Ra/Rg = 493 ~ 100 ppm), fast recovery (τrec = 22 s), and low detection limit (LOD = 11.3 ppb). Density functional theory calculations delineate that TEA binds preferentially to the Ru-In2O3 surface with a much larger adsorption energy than that of TEA on bare In2O3 or other gas molecules on Ru-In2O3, supporting the enhanced sensitivity and selectivity achieved by introducing Ru. Furthermore, a smart gas sensing system based on Ru-In2O3-0.8 material demonstrates real-time half-fin anchovy freshness monitoring application on mobile phone. This work not only proposes the structure modulations for exploration of advanced sensing materials, but also guides the potential for real-time analysis, monitoring and diagnosis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"39 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145955864","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}
Huan Wang, Hao-Lan Zhang, Yan-Cong Chen, Tao Shang, Ming Liu, Xiao-Han Peng, Ying Liu, Ming-Liang Tong, Fu-Sheng Guo
Even for a simple bimetallic rare-earth single-molecule magnet (SMM), the parallel alignment of the local anisotropy axes with the axis connecting the two rare-earth ions is still a significant synthetic challenge and rarely achieved. Here, by utilizing the dianionic compound [Na2(C4B)Et4Me2N(THF)2]2, we present the first synthesis and comprehensive characterization of a series of rare-earth(III) inverse-sandwich compounds with the chemical formula as [(μ:η5:η5-(C4B)Et4Me2N)RE2(BH4)4(THF)2]·toluene (1-RE), where RE = Gd, Dy, Y; (C4B)Et4Me2N = 1-(N,N-dimethylamino)-2,3,4,5-tetraethylborolyl; THF = tetrahydrofuran. Magnetic investigations confirm the existence of strong antiferromagnetic exchange interactions (J = −0.56 cm−1 for 1-Gd) in compounds 1-Gd and 1-Dy, indicating that the dianionic five-membered aromatic ligand is an advantageous bridge to enhance the exchange interactions between the rare-earth centers. The dilution treatment of Dy analogue (1-Dy@Y) reveals that the magnetic interactions between Dy(III) ions are capable of effectively suppressing the quantum tunneling of magnetization. Theoretical calculations on 1-Dy demonstrate that the local anisotropy axes are almost colinear to the axis connecting the two dysprosium ions. This work provides the first rare-earth inverse sandwich compounds supported by a dianionic five-membered aromatic ligand, and further reveals the opportunities for the synthesis of high-performing polynuclear rare-earth SMMs with a similar strategy.
{"title":"Rare-Earth Inverse Sandwich Compounds Supported by A Dianionic Five-Membered Aromatic Ligand","authors":"Huan Wang, Hao-Lan Zhang, Yan-Cong Chen, Tao Shang, Ming Liu, Xiao-Han Peng, Ying Liu, Ming-Liang Tong, Fu-Sheng Guo","doi":"10.1039/d5qi02360b","DOIUrl":"https://doi.org/10.1039/d5qi02360b","url":null,"abstract":"Even for a simple bimetallic rare-earth single-molecule magnet (SMM), the parallel alignment of the local anisotropy axes with the axis connecting the two rare-earth ions is still a significant synthetic challenge and rarely achieved. Here, by utilizing the dianionic compound [Na2(C4B)Et4Me2N(THF)2]2, we present the first synthesis and comprehensive characterization of a series of rare-earth(III) inverse-sandwich compounds with the chemical formula as [(μ:η5:η5-(C4B)Et4Me2N)RE2(BH4)4(THF)2]·toluene (1-RE), where RE = Gd, Dy, Y; (C4B)Et4Me2N = 1-(N,N-dimethylamino)-2,3,4,5-tetraethylborolyl; THF = tetrahydrofuran. Magnetic investigations confirm the existence of strong antiferromagnetic exchange interactions (J = −0.56 cm−1 for 1-Gd) in compounds 1-Gd and 1-Dy, indicating that the dianionic five-membered aromatic ligand is an advantageous bridge to enhance the exchange interactions between the rare-earth centers. The dilution treatment of Dy analogue (1-Dy@Y) reveals that the magnetic interactions between Dy(III) ions are capable of effectively suppressing the quantum tunneling of magnetization. Theoretical calculations on 1-Dy demonstrate that the local anisotropy axes are almost colinear to the axis connecting the two dysprosium ions. This work provides the first rare-earth inverse sandwich compounds supported by a dianionic five-membered aromatic ligand, and further reveals the opportunities for the synthesis of high-performing polynuclear rare-earth SMMs with a similar strategy.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938096","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}
Yongmei Hua, Fengming Ma, Jiaqi Gu, Huizi Songtian, Fan Zhou, Lu Yang, Xiang Fang, Lulu Mu, Xulai Yang, Peng Yin, Jinjin Li, Qiye Zheng, Jinyun Liu
Sodium-ion (Na-ion) batteries are attractive for large-scale storage owing to the abundance of Na, its ionization energy comparable to Li, and the low Na+/Na redox potential. However, currently available anode materials remain suboptimal, limited by sluggish ion/electron transport and large volume changes during cycling. Here, we report a heterostructured binary sulfides/carbon (Cu7S4/Co9S8/C) polyhedron for Na-ion battery anode, which exhibits high performance across diverse cycling rates and temperatures. In situ X-ray diffraction and Raman spectroscopy demonstrate reversible structural evolution during cycling. Cu7S4/Co9S8/C anode achieves a high capacity of 556 mAh g-1 after 300 cycles at 0.5 A g-1 with a Coulombic efficiency > 99%, and maintains 508 mAh g-1 after 1300 cycles at 3.0 A g-1. It also exhibits strong thermal tolerance, retaining 486 mAh g-1 after 500 cycles at 50 °C. Moreover, pairing Cu7S4/Co9S8/C anode with a NaVPO4 cathode yields excellent full-cell performance, underscoring practical potential. To further evaluate the thermal properties, 3ω method is employed to quantify the effective thermal conductivity of the composite. The Cu7S4/Co9S8/C architecture delivers a thermal conductivity of 0.30 W m-1 K-1, improving by ~25% and ~20% over Cu7S4/C and Co9S8/C, respectively. These findings highlight a generalizable heterostructure design strategy for high-performance anodes and provide guidance for engineering energy-storage materials and safe secondary batteries.
钠离子（Na-ion）电池由于其丰富的Na，其电离能与Li相当，以及低Na+/Na氧化还原电位而具有大规模存储的吸引力。然而，目前可用的阳极材料仍然不是最理想的，受到离子/电子传输缓慢和循环过程中体积变化大的限制。在这里，我们报道了一种用于钠离子电池阳极的异质结构二元硫化物/碳（Cu7S4/Co9S8/C）多面体，该多面体在不同的循环速率和温度下都表现出高性能。原位x射线衍射和拉曼光谱证明了循环过程中可逆的结构演化。Cu7S4/Co9S8/C阳极在0.5 a g-1下循环300次后可获得556 mAh g-1的高容量，库仑效率>； 99%，在3.0 a g-1下循环1300次后可保持508 mAh g-1。它还具有很强的耐热性，在50°C下500次循环后保持486 mAh g-1。此外，将Cu7S4/Co9S8/C阳极与NaVPO4阴极配对可以获得出色的全电池性能，强调了实用潜力。为了进一步评价复合材料的热性能，采用3ω法量化复合材料的有效导热系数。Cu7S4/Co9S8/C的导热系数为0.30 W m-1 K-1，比Cu7S4/C和Co9S8/C分别提高了25%和20%。这些发现为高性能阳极的异质结构设计提供了一种可推广的策略，并为工程储能材料和安全二次电池提供了指导。
{"title":"Designing a binary sulfides/carbon polyhedron for secondary batteries with high electrochemical and thermal performances","authors":"Yongmei Hua, Fengming Ma, Jiaqi Gu, Huizi Songtian, Fan Zhou, Lu Yang, Xiang Fang, Lulu Mu, Xulai Yang, Peng Yin, Jinjin Li, Qiye Zheng, Jinyun Liu","doi":"10.1039/d5qi02190a","DOIUrl":"https://doi.org/10.1039/d5qi02190a","url":null,"abstract":"Sodium-ion (Na-ion) batteries are attractive for large-scale storage owing to the abundance of Na, its ionization energy comparable to Li, and the low Na+/Na redox potential. However, currently available anode materials remain suboptimal, limited by sluggish ion/electron transport and large volume changes during cycling. Here, we report a heterostructured binary sulfides/carbon (Cu7S4/Co9S8/C) polyhedron for Na-ion battery anode, which exhibits high performance across diverse cycling rates and temperatures. In situ X-ray diffraction and Raman spectroscopy demonstrate reversible structural evolution during cycling. Cu7S4/Co9S8/C anode achieves a high capacity of 556 mAh g-1 after 300 cycles at 0.5 A g-1 with a Coulombic efficiency > 99%, and maintains 508 mAh g-1 after 1300 cycles at 3.0 A g-1. It also exhibits strong thermal tolerance, retaining 486 mAh g-1 after 500 cycles at 50 °C. Moreover, pairing Cu7S4/Co9S8/C anode with a NaVPO4 cathode yields excellent full-cell performance, underscoring practical potential. To further evaluate the thermal properties, 3ω method is employed to quantify the effective thermal conductivity of the composite. The Cu7S4/Co9S8/C architecture delivers a thermal conductivity of 0.30 W m-1 K-1, improving by ~25% and ~20% over Cu7S4/C and Co9S8/C, respectively. These findings highlight a generalizable heterostructure design strategy for high-performance anodes and provide guidance for engineering energy-storage materials and safe secondary batteries.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938118","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}
Oliver Lange, Florian Doettinger, Lars E. Burmeister, Johannes Pascal Zurwellen, Toni M. Maier, Christian Kleeberg, Michael Karnahl, Christoph R Jacob, Stefanie Tschierlei
A modular design approach for bichromophoric Cu(I) complexes is reported, combining a [Cu(N^N)(P^P)]⁺ scaffold that supports metal-to-ligand charge transfer with two polycyclic aromatic hydrocarbon chromophores covalently attached to the diimine ligand. Three new systems incorporating 9,9-dimethyl-9H-fluorene, phenanthrene, and anthracene units at the 4,7-positions of neocuproine were synthesized and fully characterized. Structural analysis reveals twisted geometries of the attached chromophores, which reduce conjugation with the diimine core. Electrochemical measurements indicate only moderate shifts in reduction potentials, indicating preservation of the Cu(I)-centered redox behavior. Across the series, the visible MLCT band is retained without pronounced red-shifts, while the molar attenuation coefficients increase markedly (x1.7-3.4 vs. the reference), in line with calculated oscillator strengths. Fragment comparisons and computations attribute the additional UV intensity to intraligand charge transfer (9,9-dimethyl-9H-fluorene, phenanthrene) and to vibronically structured π*A ← πA transitions (anthracene), consistent with the non-coplanar geometries. Complexes bearing 9,9-dimethyl-9H-fluorene and phenanthrene substituents exhibit yellow emission involving the Cu(I)-based metal-to-ligand charge transfer state (λem ≈ 565 nm, τ up to 20.8 μs), whereas the anthracene-substituted system populates a non-emissive ³ππ* triplet state localized on an anthracene moiety (τ > 35 μs), as evidenced by transient absorption spectroscopy and time-dependent density functional theory. These results establish clear structure-property relationships in bichromophoric Cu(I) systems and illustrate how polycyclic aromatic hydrocarbon chromophores influence excited-state character and dynamics.
{"title":"Polycyclic Aromatic Hydrocarbon Chromophores Tune Photophysical Properties in Bichromophoric Cu(I) Photosensitizers","authors":"Oliver Lange, Florian Doettinger, Lars E. Burmeister, Johannes Pascal Zurwellen, Toni M. Maier, Christian Kleeberg, Michael Karnahl, Christoph R Jacob, Stefanie Tschierlei","doi":"10.1039/d5qi02274f","DOIUrl":"https://doi.org/10.1039/d5qi02274f","url":null,"abstract":"A modular design approach for bichromophoric Cu(I) complexes is reported, combining a [Cu(N^N)(P^P)]⁺ scaffold that supports metal-to-ligand charge transfer with two polycyclic aromatic hydrocarbon chromophores covalently attached to the diimine ligand. Three new systems incorporating 9,9-dimethyl-9H-fluorene, phenanthrene, and anthracene units at the 4,7-positions of neocuproine were synthesized and fully characterized. Structural analysis reveals twisted geometries of the attached chromophores, which reduce conjugation with the diimine core. Electrochemical measurements indicate only moderate shifts in reduction potentials, indicating preservation of the Cu(I)-centered redox behavior. Across the series, the visible MLCT band is retained without pronounced red-shifts, while the molar attenuation coefficients increase markedly (x1.7-3.4 vs. the reference), in line with calculated oscillator strengths. Fragment comparisons and computations attribute the additional UV intensity to intraligand charge transfer (9,9-dimethyl-9H-fluorene, phenanthrene) and to vibronically structured π*A ← πA transitions (anthracene), consistent with the non-coplanar geometries. Complexes bearing 9,9-dimethyl-9H-fluorene and phenanthrene substituents exhibit yellow emission involving the Cu(I)-based metal-to-ligand charge transfer state (λem ≈ 565 nm, τ up to 20.8 μs), whereas the anthracene-substituted system populates a non-emissive ³ππ* triplet state localized on an anthracene moiety (τ > 35 μs), as evidenced by transient absorption spectroscopy and time-dependent density functional theory. These results establish clear structure-property relationships in bichromophoric Cu(I) systems and illustrate how polycyclic aromatic hydrocarbon chromophores influence excited-state character and dynamics.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"252 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938120","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}
In the field of metallo-organic helicates, the controlled synthesis of low-symmetric structures remains a significant challenge on the precise control over the self-assembly process due to their thermodynamically disfavored nature, compared to highly symmetric forms. This study introduces an effective strategy by shifting the design focus from ligands to metal centers. Through precise regulation of the stereoconfiguration, two metal centers are directed to adopt opposite handedness, affording a mesomeric and C1 symmetric helicate structure S, fully characterized by 1H NMR, ESI-MS and SC-XRD. The resulting helicate structure features a well-defined square cavity with a 8.5 Å distance between roof and floor, is capable of accommodating planar polycyclic aromatic hydrocarbons (PAHs) via π–π stacking interaction within optimal range after slight compression. More importantly, the binding constants shows a proportional enhancement with the increasing of number of π-electrons in PAH guests. This work points toward new direction for developing functional low-symmetric metallo-organic supramolecular assemblies. And, the clear structure-function relationship highlights its potential applications in molecular separation and sensing.
{"title":"Controllable self-assembly of mesomeric metallo-organic helicate and its π-electron number dependent encapsulation of polycyclic aromatic hydrocarbons (PAHs)","authors":"huoqing Chen, Haoxuan Xu, Tun Wu, Yuming Guan, Qingwu Long, Qixia Bai, Tian Li, Tian-Yu Liu, Pingshan Wang, Zhe Zhang","doi":"10.1039/d5qi02447a","DOIUrl":"https://doi.org/10.1039/d5qi02447a","url":null,"abstract":"In the field of metallo-organic helicates, the controlled synthesis of low-symmetric structures remains a significant challenge on the precise control over the self-assembly process due to their thermodynamically disfavored nature, compared to highly symmetric forms. This study introduces an effective strategy by shifting the design focus from ligands to metal centers. Through precise regulation of the stereoconfiguration, two metal centers are directed to adopt opposite handedness, affording a <em>mesomeric</em> and <em>C</em><small><sub>1</sub></small> symmetric helicate structure <strong>S</strong>, fully characterized by <small><sup>1</sup></small>H NMR, ESI-MS and SC-XRD. The resulting helicate structure features a well-defined square cavity with a 8.5 Å distance between roof and floor, is capable of accommodating planar polycyclic aromatic hydrocarbons (PAHs) via π–π stacking interaction within optimal range after slight compression. More importantly, the binding constants shows a proportional enhancement with the increasing of number of π-electrons in PAH guests. This work points toward new direction for developing functional low-symmetric metallo-organic supramolecular assemblies. And, the clear structure-function relationship highlights its potential applications in molecular separation and sensing.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"94 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145938121","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}
During the water splitting process for hydrogen production with metal hydroxide electrocatalysts, a self-reconstructing reaction occurring at low potential is the key to efficient operations. In this work, a Ni-Fe(OH)₃ electrocatalyst is designed, in which the built-in electric field formed at the heterojunction results in electron accumulation on Ni and facilitates the reconstruction of Fe(OH)₃ into active FeOOH under a lower applied potential while maintaining structural stable. Triggered by the interfacial electron accumulation and structural reconstruction, the prepared Ni-Fe(OH)₃ anchored on an iron-nickel-foam substrate shows an overpotential of just 453 mV that can drive an ampere level current of 1.0 A cm⁻² in 1.0 M KOH mixed seawater, with remarkable stability for over 360 h. Density functional theory calculations suggest that the in-situ reconstructed Ni-FeOOH enhances the adsorption behavior of intermediates and significantly reduces the energy barrier of the oxygen revolution reaction. These results underscore the great promise of engineering built-in electric field in transition metal hydroxide catalysts for efficient hydrogen production via seawater oxidation。
在金属氢氧化物电催化剂水解制氢过程中，低电位下的自重构反应是高效运行的关键。在这项工作中，设计了一种Ni-Fe（OH）₃电催化剂，其中在异质结处形成的内置电场导致电子在Ni上积聚，并且有利于Fe（OH）₃在较低的施加电位下重构为活性FeOOH，同时保持结构稳定。在界面电子积累和结构重建的触发下，制备的Ni-Fe（OH）₃锚定在铁镍泡沫基板上，其过电位仅为453 mV，在1.0 M KOH混合海水中可以驱动1.0 A cm⁻²的安培电流。密度泛函理论计算表明，原位重构的Ni-FeOOH增强了中间体的吸附行为，显著降低了氧旋转反应的能垒。这些结果强调了工程内置电场在过渡金属氢氧化物催化剂中用于通过海水氧化高效制氢的巨大前景。
{"title":"Built-in electric field triggered interfacial electron accumulation and structural reconstruction for boosting ampere-level-current seawater oxidation","authors":"Xueling Wei, Youjun Huang, Qiguan Wang, Linlin Dang, Xiangyu Zou, Wenhu Li, Taotao Ai, Sumin Wang","doi":"10.1039/d5qi02143j","DOIUrl":"https://doi.org/10.1039/d5qi02143j","url":null,"abstract":"During the water splitting process for hydrogen production with metal hydroxide electrocatalysts, a self-reconstructing reaction occurring at low potential is the key to efficient operations. In this work, a Ni-Fe(OH)₃ electrocatalyst is designed, in which the built-in electric field formed at the heterojunction results in electron accumulation on Ni and facilitates the reconstruction of Fe(OH)₃ into active FeOOH under a lower applied potential while maintaining structural stable. Triggered by the interfacial electron accumulation and structural reconstruction, the prepared Ni-Fe(OH)₃ anchored on an iron-nickel-foam substrate shows an overpotential of just 453 mV that can drive an ampere level current of 1.0 A cm⁻² in 1.0 M KOH mixed seawater, with remarkable stability for over 360 h. Density functional theory calculations suggest that the in-situ reconstructed Ni-FeOOH enhances the adsorption behavior of intermediates and significantly reduces the energy barrier of the oxygen revolution reaction. These results underscore the great promise of engineering built-in electric field in transition metal hydroxide catalysts for efficient hydrogen production via seawater oxidation。","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"39 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145907970","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：