Inorganic Chemistry Frontiers最新文献

{"title":"Dual-Emission-Center Strategy in Ca3Ga4O9:Er3+/Sm3+ Enables Color-Tunable Afterglow for Multimodal Luminescent Encryption Materials","authors":"Yunfei Wang, Sixia Li, Yuzhu Yang, Peng Zhang, Wenfei Qin, Sai Zhou, Xuan Miao, Zenggang Lin, Wei-Sheng Liu","doi":"10.1039/d5qi01359c","DOIUrl":"https://doi.org/10.1039/d5qi01359c","url":null,"abstract":"Materials exhibiting long-persistent luminescence (LPL) in the visible spectrum hold pivotal importance for anti-counterfeiting and encryption. Nevertheless, conventional LPL materials typically only exhibit single-color afterglow emission. This constraint makes it imperative to develop multimodal luminescent systems featuring spectrally tunable afterglow. Herein, the Er3+/Sm3+ co-doped Ca3Ga4O9 phosphors achieve multicolor photoluminescence (PL), upconversion luminescence (UCL), and color-tunable LPL by responding to multiple excitations modes ranging from ultraviolet (UV) to near-infrared radiation (NIR). Spectral analysis reveals a green-to-orange multicolor afterglow by varying the relative concentrations of Er3+ and Sm3+ ions. To unravel the mechanism of multicolor afterglow, afterglow spectra and thermoluminescence (TL) spectra are systematically employed to probe the trap distribution mediated by Er3+ and Sm3+ co-doping. Finally, their prospective application in optical anti-counterfeiting and information encryption is also systematically investigated based on the color-tunable LPL. This successful integration of multicolor, multimodal luminescence with color-tunable afterglow in a single host provides a novel platform for anti-counterfeiting and encryption, significantly expanding the visual diversity of displayable information.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924151","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}

{"title":"Chiral molecular 4f qubits by post functionalization","authors":"Steen H. Hansen, Christian D. Buch, Bela E. Bode, Stergios Piligkos","doi":"10.1039/d5qi00977d","DOIUrl":"https://doi.org/10.1039/d5qi00977d","url":null,"abstract":"We herein demonstrate the synthesis of a pair of enantiomerically pure Yb<small>^III</small> complexes by post-functionalisation of the parent Yb<small>^III</small> complex <em>via</em> condensation with an enantiomerically pure chiral amine. The enantiomeric pair is structurally characterised by single crystal and powder X-ray diffraction, showing that it crystalises in the <em>P</em>2<small>₁</small>2<small>₁</small>2<small>₁</small> Sohncke space group with Flack parameters close to zero, which confirms their enantiopurity. Circular Dichroism (CD) and absorption spectroscopies in the NIR reveal sharp <small>²</small>F<small>_7/2</small> → <small>²</small>F<small>_5/2</small> f–f transitions, with <em>g</em><small>_abs</small> values up to 0.07, indicating a chiral environment for the ytterbium centre. Furthermore, a dynamic mechanism with mixing of ligand states is shown to contribute to the CD intensity. X-band pulse Electron Paramagnetic Resonance spectroscopy, on a magnetically dilute single crystal containing 1% of Yb<small>^III</small> complexes within the isostructural Y<small>^III</small> diamagnetic host, reveals a phase memory time, <em>T</em><small>_m</small>, of the electronic spin of 600 ns and that it can be coherently manipulated by microwave pulses, as evidenced by Rabi nutations.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"58 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928195","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}

{"title":"Energy-Transfer Enhanced Cr3+/Ni2+ Co-doped Tantalate Phosphors For Broadband NIR pc-LED Applications","authors":"Muji Hala, Yu Zhang, Kai Li, Qixu Tian, Lig Sur, Ze Wang, Xinyu Gu, Mai Nari, Yuansong Gao, Kefu Chao, Bingfu Lei","doi":"10.1039/d5qi01495f","DOIUrl":"https://doi.org/10.1039/d5qi01495f","url":null,"abstract":"Near-infrared (NIR) emitting materials have garnered significant interest for their excellent performance in optical imaging, optical temperature sensing, non-destructive testing, and other fields. In this paper presents a near-infrared (NIR) material, Mg<small>₂</small>LaTaO<small>₆</small> (MLTO): Cr<small>³⁺</small>,Ni<small>²⁺</small>, synthesized using the high temperature solid-state method. When excited at 468 nm, the material exhibits broadband emission from 700 to 1600 nm with a full width at half maximum (FWHM) of 1232 cm<small>^-1</small>. The Cr<small>³⁺</small> → Ni<small>²⁺</small> energy transfer (ET) significantly enhances Ni<small>²⁺</small> emission，increasing its intensity by 2.85 times at 1336 nm and ET efficiency of 79%.The material also demonstrates excellent thermal stability, retaining 87% of its emission intensity at 423 K. By integrating the phosphor with a 460 nm blue light chip, a NIR pc-LED was successfully fabricated, showing potential for applications in medical imaging, information encryption, organic compound identification, and fruit freshness detection. The co-doping strategy of Cr<small>³⁺</small> and Ni<small>²⁺</small> effectively solves the issue of Ni<small>²⁺</small> emission being difficult to excite with blue light, offering a novel design strategy for the development of wideband NIR pc-LED based on blue light LED chips.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144924152","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}

{"title":"Catalyst design for electrochemical selective oxidation of aldehydes to carboxylic acids","authors":"Yanxue Chao, Jiani Han, Yaodong Yu, Jianping Lai, Lei Wang","doi":"10.1039/d5qi01343g","DOIUrl":"https://doi.org/10.1039/d5qi01343g","url":null,"abstract":"In the global carbon neutrality context, green hydrogen, a key carrier of clean energy, requires urgent breakthroughs in production technology. In water electrolysis, the high energy consumption and low efficiency of the oxygen evolution reaction (OER) at the anode severely limit overall energy conversion efficiency. The electrocatalytic selective oxidation of aldehydes shows potential to replace the OER due to its low thermodynamic potential and fast kinetics, and it can transform aldehydes into high-value carboxylic acids through precise catalyst control. This paper reviews catalyst design strategies for this process, focusing on reaction mechanisms, design principles, and structure–performance relationships. By analyzing the activation of C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>O bonds and C–H bond cleavage kinetics, core design principles based on electronic structure regulation and synergistic effects are proposed, and a catalyst performance model is established using <em>in situ</em> characterization and theoretical calculations. This provides theoretical guidance for designing efficient catalysts and prospects for future research directions, such as non-precious metal catalyst development and complex reaction network regulation, offering new ideas for the industrial application of “green hydrogen–high-value chemicals” co-production technology.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"16 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144928193","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}

{"title":"Mechanistic Insights into Au(I)(NHC)Cl Targeting of the HIV-NCp7 Zinc Finger via Metadynamics Simulations","authors":"Gustavo Clauss Rodrigues, Camilla Abbehausen, Stefano Leoni","doi":"10.1039/d5qi01601k","DOIUrl":"https://doi.org/10.1039/d5qi01601k","url":null,"abstract":"Zinc fingers (ZFs) regulate important metabolic pathways. Their inhibition in cancer cells or pathogenic viruses and protozoa can be achieved with transition metal-based compounds, including gold complexes. However, selectively targeting specific ZFs can be challenging, due also to the structural diversity of ZFs and to the lack of mechanistic details. Here, metadynamics simulations were employed to investigate the mechanism of interaction between the [Au(I)(NHC)Cl] complex and the zinc finger region of HIV-NCp7, which comprises two zinc finger domains essential for the protein’s function and the viral life cycle. The simulations revealed that the two zinc finger cores exhibit markedly different reactivities. Specifically, the C-terminal zinc finger, with Cys49 as the target residue, was identified as the primary site for Au(I) binding. Additionally, the simulations uncovered acid-base steps, induced by the [Au(I)(NHC)]+ species, that facilitate thiolate coordination of Cys39 to the Au(I)(NHC) complex. These events also promote conformational changes, including widening of the zinc finger core, enabling water access to the zinc centre.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144918965","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}

{"title":"Mn(II)-aqua-decavanadate: a bifunctional homogeneous electrocatalyst for hydrogen evolution- and oxygen reduction-reaction","authors":"Debu Jana, Rachapudi Phebe Florance, Rabin Kumar Poria, Samar K Das","doi":"10.1039/d5qi01273b","DOIUrl":"https://doi.org/10.1039/d5qi01273b","url":null,"abstract":"Abstract. Although the organic-inorganic hybrid Mn-containing decavanadate single crystals are reported, surprisingly, there is no report on organic-free Mn-containing decavanadate-based single crystals. In this work, we have achieved isolating pure inorganic single crystals of manganese containing decavanadate compound K2[Mn(H2O)6]2[V10O28] (1). This water-soluble compound (1) has unambiguously been characterized by single-crystal X-ray crystallography, including routine spectroscopic and microscopic analyses. Interestingly, compound 1 acts as a bifunctional homogeneous electrocatalyst for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) in an acidic aqueous solution without its decomposition (or electrodeposition). Notably, in the case of HER, homogeneous solutions (identical condition) of individual components [V10O28]6- (i.e., Na6[V10O28]) and [Mn(H2O)6]2+ (e.g., MnCl2‧6H2O) do not exhibit electrocatalytic HER activity, even though these two components are the primary sub-units of compound 1. However, the synergy of [V10O28]6- with [Mn(H2O)6]2+ within the crystal matrix enhances the stability and significantly increases the homogeneous electrocatalytic HER activity of compound 1. Experiments involving ORR utilizing a rotating ring-disc electrode (RRDE) have validated the electrochemical production of H2O through four-electron reduction of molecular oxygen. Compound 1 shows a better electrocatalytic ORR activity as compared with those of homogeneous solutions (identical condition) of individual [V10O28]6- and [Mn(H2O)6]2+components of compound 1 indicating a synergy between [V10O28]6- and [Mn(H2O)6]2+ within the crystal matrix.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-08-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144918967","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}

{"title":"Fast and selective protein modification with iron-substituted polyoxometalates via a radical pathway","authors":"Mhamad Aly Moussawi, Shorok A. M. Abdelhameed, Francisco de Azambuja, Andy Wijten, Tamara Vasović, Tanja Ćirković Veličković, Tatjana N. Parac-Vogt","doi":"10.1039/d5qi01454a","DOIUrl":"https://doi.org/10.1039/d5qi01454a","url":null,"abstract":"Oxidative modifications of proteins are crucial post-translational modifications that profoundly impact their structure, function, and turnover. Developing chemical methods that selectively induce oxidative protein modifications and cleavage would significantly facilitate elucidation of these oxidative processes, benefiting our understanding of disease mechanisms, identifying novel therapeutic targets, and advancing biotechnological applications. In this work, we demonstrate that all-inorganic discrete polyoxometalate (POM) clusters stabilize redox active metal centers such as Fe(<small>III</small>) and Mn(<small>III</small>) under physiological pH and temperature (pH = 7.5, 37 °C), enabling the generation of reactive oxygen species (ROS) under mild aqueous conditions. Specifically, we show that catalytic amounts of the iron-substituted POM K<small>₇</small>[Fe<small>^III</small>(α<small>₂</small>-P<small>₂</small>W<small>₁₇</small>O<small>₆₁</small>)(H<small>₂</small>O)] (Fe<small>^III</small>WD), in the presence of ascorbate (Asc), rapidly induce selective oxidation and cleavage of hen egg-white lysozyme (HEWL) in four narrow regions of the protein sequence. The protein cleavage sites are all located near the interaction sites of M<small>^III</small>WD (M = Mn or Fe) catalysts with the protein surface. In contrast, the manganese-substituted POM K<small>₇</small>[Mn<small>^III</small>(α<small>₂</small>-P<small>₂</small>W<small>₁₇</small>O<small>₆₁</small>)(H<small>₂</small>O)] (Mn<small>^III</small>WD) shows no similar catalytic activity, pointing towards a different radical mechanism. These findings highlight the potential of well-tailored inorganic clusters to facilitate selective catalytic processes, enabling iron to target specific regions of a protein sequence without relying on coordination sites on the protein surface, while offering flexibility in reaction conditions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911017","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}

{"title":"How Structural Dynamics Influence the Substrate Oxidation Energetics in Lytic Polysaccharide Monooxygenase","authors":"Marlisa Muriel Hagemann, Ulf Ryde, Erik Donovan Hedegård","doi":"10.1039/d5qi01590a","DOIUrl":"https://doi.org/10.1039/d5qi01590a","url":null,"abstract":"Lytic polysaccharide monooxygenases (LPMOs) are copper-dependent enzymes that have fueled the hope for sustainable biofuel production since they enhance the breakdown of recalcitrant polysaccharides like cellulose. In the consensus mechanism, their catalytic activity relies on forming an 'oxyl', [CuO <small>^•–</small>]<small>⁺</small> , species at the active site, followed by subsequent hydrogen atom abstraction (HAA) from the substrate. Some studies report rather high barriers for this reaction, identifying it as the rate-limiting step in the oxidation process, whereas other investigations have reported significantly lower barriers. In this study, we have constructed a force field for the active site and show through extensive sampling from MD simulations that the QM/MM reaction barrier depend critically on the underlying structural conformations of the enzyme–substrate complex. The results support low energy barriers for the HAA step and help to explain previous discrepancies in the literature, which may be attributed to insufficient conformational sampling.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911020","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}

{"title":"Decorating highly-conjugated and electron-rich Co-MOF with Ni3S2 for improved oxygen evolution and urea oxidation reactions","authors":"Li-Wen Wang, Xuan Jing, Sifu Tang","doi":"10.1039/d5qi01534k","DOIUrl":"https://doi.org/10.1039/d5qi01534k","url":null,"abstract":"The development of high-performance non-noble metal electrocatalysts for water splitting is critical for sustainable hydrogen production but remains challenging due to the moderate activity, sluggish kinetics, and unsatisfying durability of oxygen evolution reaction catalysts. To overcome these limitations, this work integrates rigid conjugated metal-organic frameworks with heterointerface engineering to boost electrocatalytic performance. Furthermore, substituting the energy-intensive OER with the urea oxidation reaction presents a promising approach to lower energy consumption. Herein, we design and synthesize a composite catalyst, Ni3S2-CoFcDCA/NF, comprising Ni3S2 and a cobalt ferrocenedicarboxylate MOF. The synergistic interaction between Ni3S2 and CoFcDCA not only enhances electron transfer but also exposes abundant active sites, resulting in exceptional OER and UOR performance. The catalyst achieves a current density of 50 mA cm−2 at remarkably low overpotentials of 202 mV for OER and 1.39 V for UOR in alkaline media. Density functional theory calculations reveal that the optimized d-band center position in NiOOH/CoFcDCA regulates the adsorption energetics of oxygen intermediates, particularly lowering the activation barrier for the OH* → O* transition, thereby accelerating the OER kinetics. This study highlights the potential of heterostructured MOF-based catalysts for efficient water splitting and offers valuable guidance for designing cost-effective non-noble metal electrocatalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911019","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}

{"title":"Magnetic Dynamics and Exchange Coupling in Dinuclear Lanthanide Complexes Bridged by Naphthoquinone and Anthraquinone Radicals","authors":"Dimitris I Alexandropoulos, Kuduva R. Vignesh, Luis Cunha-Silva, Kim R. Dunbar","doi":"10.1039/d5qi01477h","DOIUrl":"https://doi.org/10.1039/d5qi01477h","url":null,"abstract":"The use of the bis(bidentate) quinoid ligands 5,8-Dihydroxy-1,4-naphthoquinone (dhnqH2) and 1,5-Dihydroxyanthraquinone (dhaqH2) in Ln chemistry has afforded four new dinuclear DyIII complexes, viz., [Dy2(dhnq)(Tpz)4].6CH2Cl2 (1.6CH2Cl2), [Dy2(dhaq)(Tpz)4].6CH2Cl2 (2.6CH2Cl2), {K(18-crown-6)}[Dy2(dhnq)(Tpz)4].2THF (3.2THF) and {K(18-crown-6)}[Dy2(dhaq)(Tpz)4].2THF (4.2THF) (Tpz = tris(pyrazolyl)borate). In compounds 1 and 2 the DyIII ions are bridged by the diamagnetic dianionic forms of dhnq2- and dhaq2, while complexes 3 and 4 are bridged the one-electron reduced, radical forms of these ligands. The presence of the ligand-centered radical has been confirmed by X-ray crystallography and SQUID magnetometry. Alternating current (ac) magnetic susceptibility studies revealed that the relaxation dynamics of 1 and 2 are primarily governed by fast quantum tunneling of magnetization (QTM). Conversely, the radical-bridged complexes 3 and 4 behave as single-molecule magnets (SMMs) with energy barriers for the magnetization reversal, Ueff, of 24.17 K and 16.70 K, respectively, in the absence of a direct current (dc) applied field. The strong ferromagnetic Dy-radical interactions, computed using ab initio POLY_ANISO calculations, led to coupling constants of J = +5.0 and +1.2 cm⁻¹ for 3 and 4, respectively, which explains the SMM behavior in these complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911018","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}