Inorganic Chemistry Frontiers最新文献

{"title":"Multidentate-Phosphine Unlocks Active Ag Sites in Pt/PdAg14 Nanoclusters for Efficient Electrocatalytic Nitrate Reduction","authors":"Manman Zhou,Xuhui Ding,Qian Cheng,Yuanxin Du,Shan Jin,lin xiong,Yahui Li,Xu-Cheng Fu,Manzhou Zhu","doi":"10.1039/d6qi02081j","DOIUrl":"https://doi.org/10.1039/d6qi02081j","url":null,"abstract":"Catalysts with stable structures and exposed active sites are highly desirable for optimizing catalytic performance, yet their rational design remains a critical challenge in the field. Herein, we demonstrate that the diphosphine ligand 1,4bis(diphenylphosphino)butane (Dppb) can effectively trigger the exposure of active sites on the reported Pt/PdAg14(PR3)8(SR)6 nanoclusters, thereby inducing their structural transformation into Pt/PdAg14(Dppb)3(SR)6 nanoclusters.Benefiting from their unsaturated coordination environment and favorable electronic properties, the non-phosphinecoordinated Ag(SR)3 metal motifs serve as the dominant active centers for the electrocatalytic nitrate reduction reaction (NO3RR), which significantly facilitates the adsorption and activation of NO3 -. Notably, the core Pd and Pt atoms regulate the electronic configuration of the nanoclusters to promote the adsorption and activation of reaction intermediates, among which Pd doping exhibits superior modulation performance compared to Pt doping. This work not only clarifies the structureactivity relationship of ligand-engineered nanocatalysts but also highlights the synergistic strategy of ligand-regulated active site exposure and heteroatom doping as an effective approach for developing high-performance nanocatalysts toward sustainable environmental applications.2","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173172","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":"Nano-biochemical sensors for trace uranyl detection: Advances in Recognition elements and signal output strategies","authors":"Zhen Zhen,Jiaqi Cui,Xiao Tan,Lima Ge,Yunlong Bai,Ruibing Feng,Weiqiang Tan,Jie Niu,Guo-Dong Li,Huining Chai,Guangyao Zhang","doi":"10.1039/d6qi02017h","DOIUrl":"https://doi.org/10.1039/d6qi02017h","url":null,"abstract":"Uranium is a strategic resource for the nuclear industry, but its mining and utilization can cause environmental contamination. In aquatic environments, the highly stable and soluble uranyl ion (UO22+) exhibits both chemical toxicity and radioactivity, posing serious threats to ecosystems and human health. Accordingly, rapid, highly sensitive, and anti-interference detection of UO22+ has become a major focus in nano-biochemical sensing. This review systematically summarizes recent advances in specific recognition strategies and signal transduction mechanisms for UO22+. From the perspective of molecular recognition, we outline the design of diverse recognition elements, including traditional coordination-based small-molecule ligands (N-donor, O-donor, S/O-mixed, and multidentate amidoxime ligands), lanthanide metal nodes, and synergistic coordination-hydrogen-bonding motifs, together with biomacromolecular and biomimetic strategies such as aptamers and molecular/ion imprinting. We further discuss how chemical recognition events are converted into readable optical or electrical outputs in UO22+ sensing systems. Representative mechanisms include nanozyme activity modulation, target-induced complex formation, and fluorescence, photoelectrochemical, or electrochemical signaling based on fluorescence resonance energy transfer, aggregation-induced emission, inner filter effect, charge transfer, and ion exchange. Finally, we highlight key challenges in applying current UO22+ biochemical sensors to complex water matrices and discuss future directions, including highly selective anti-interference materials, multimodal sensing platforms, and portable intelligent devices. This review aims to provide a theoretical basis and design guidance for next-generation high-performance platforms for trace uranium pollution monitoring.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"31 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173169","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":"An \"All-Terrain\" Ligand Design Strategy: Phosphorus-Functionalized Nickel Thiosemicarbazones for Hydrogen Evolution in Organic and Aqueous Media","authors":"Marie Poisson,Michail Papadakis,Foteini Chatzipetri,Anna Katsari,Emmanouil Nikoloudakis,Athanassios G. Coutsolelos,Maylis Orio,Renaud Hardré","doi":"10.1039/d6qi01982j","DOIUrl":"https://doi.org/10.1039/d6qi01982j","url":null,"abstract":"We report the synthesis and characterization of a series of mononuclear nickel thiosemicarbazone complexes bearing phosphorus-functionalized phenyl groups designed to improve their solubility and tune their catalytic properties for hydrogen evolution. NiTSC-PO(OEt)₂ and NiTSC-PO(OH)₂, which carry diethyl phosphonate and phosphonic acid groups, respectively, at the para position of the ligand phenyl rings, were investigated in dimethylformamide using trifluoroacetic acid as the proton source. NiTSC-PO(OH)₂ exhibited notable catalytic activity in aqueous acetate buffer and its photocatalytic performance was further evaluated in combination with nitrogen-doped carbon dots as photosensitizers and a mixture of tris(2-carboxyethyl)phosphine/ascorbic acid as sacrificial electron donor. The two complexes display complementary performances: NiTSC-PO(OEt)2 is the more active electrocatalyst in organic medium, whereas NiTSC-PO(OH)2 operates in water and under photocatalytic conditions. Ligand functionalization thus influences catalytic activity through both solubility and electronic effects, showing that a single substitution strategy can provide, within the same catalyst family, members suited to different reaction media.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149173171","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":"Isolation of Four-/Five-Coordinate Manganese(II)-Bis(dithiolene-radical): Exchange Coupling","authors":"Sujit Das,Christel L Mascarenhas,Saurav Ghosh,Sonam Suthar,Arpan Mondal,Harichandhana Elamplakkattu,Björn Schwarz,Liviu Ungur,Kartik Chandra Mondal","doi":"10.1039/d6qi01048b","DOIUrl":"https://doi.org/10.1039/d6qi01048b","url":null,"abstract":"Dithiolene ligands have long fascinated chemists for their non-innocent redox properties. The transition metal complexes with delocalized unpaired electrons on the ligand find applications in catalysis, magnetism, and molecular electronics. Despite extensive studies on Fe, Co, Ni, Pd, Pt, Mo, and W congeners featuring monoanionic dithiolene radicals, first-row analogues, particularly manganese with its versatile Mnᴵᴵ redox chemistry, remain elusive due to synthetic challenges in accessing the radical centre in the dithiolene ligand, which favours over-reduction to dianions during metallation. Here, we present two elusive manganese(II)-bis(dithiolene) diradical complexes, synthesised via a protocol that selectively generates and stabilises the monoanionic radical state, five-coordinate [Mn(II)(LS•)2(THF)] (1), alongside a four-coordinate tetrahedral [Mn(II)(LSe•)2] (2). They are unprecedented to date. Single-crystal X-ray diffraction reveals that the coordination geometries of Mn(II) ions are distorted square-pyramidal and tetrahedral in 1 and 2, respectively. These complexes were characterized by UV-VIS, IR, Raman, XPS, and EPR spectroscopy. The local spin state of Mn(II) ions, the spin ground states of the complexes and the nature of Mn(II)-radical interactions were studied by temperature-dependent magnetic susceptibility measurements. Combined magnetic and EPR measurements suggest that the central Mn(II) ion of this series of Mn(II)-bis(dithiolene)diradical complexes (1-2) most likely possesses SMn2+ = 5/2 (high spin). The central Mn(II) ions of 1-2 are antiferromagnetically coupled with two unpaired electrons on the dithiolene ligands, leading to spin ground states ST = 3/2. Broken-symmetry DFT and ab initio CASSCF calculations reproduce this spin ground state and quantify the three exchange interactions within the Radical–Mn(II)–Radical core. For 2, the CASSCF Mn–radical coupling (−44.8 cm−1) agrees with the value fitted to the magnetic data (−44.01 cm−1), and the direct radical–radical interaction is found to be negligible in tetrahedral 2 but substantial in square-pyramidal 1.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152776","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":"Gilding-inspired ultrathin metal-foil lamination for reversible zinc deposition in anode-free aqueous zinc-ion batteries","authors":"Qi-qun Lei,Zhuo Li,Wei-jia Song,Li-li Du,Peng-fei Wang,Zhe Gong,Fa-nian Shi,Kai Zhu","doi":"10.1039/d6qi02026g","DOIUrl":"https://doi.org/10.1039/d6qi02026g","url":null,"abstract":"Anode-free aqueous zinc-ion batteries (AF-AZIBs) eliminate excess metallic Zn but impose stringent requirements on Zn plating/stripping reversibility. Herein, inspired by traditional gilding, we develop an ultrathin metal-foil lamination strategy to construct Ag@Cu and Au@Cu current collectors. Comparative experiments, finite-element simulations, and density functional theory calculations show that Ag@Cu provides a more homogeneous surface and interfacial electric field, while its moderate Zn–Ag interaction and favorable interfacial kinetics promote uniform nucleation, compact growth, and reversible stripping. Consequently, Zn//Ag@Cu cells sustain 3000 cycles at 5 mA cm−2 and 1 mAh cm−2 with an average coulombic efficiency of 99.96%. The anode-free full cell pairing Ag@Cu with an electrochemically pre-zincified NH4V4O10 cathode (ZnNV) retains 96.4% of its capacity after 200 cycles at 1 A g−1, and a pouch-type cell further demonstrates larger-format feasibility. This work establishes ultrathin metal-foil lamination as an effective interface-engineering route toward highly reversible AF-AZIBs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152777","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":"Exploring C(sp)-C(sp) Kumada Cross-Coupling with Pyridinophane-supported Mn, Fe, and Co Complexes","authors":"Donghyun Jeong,Liviu M. Mirica","doi":"10.1039/d6qi01865c","DOIUrl":"https://doi.org/10.1039/d6qi01865c","url":null,"abstract":"A series of first-row transition-metal complexes bearing pyridinophane macrocycles, (RN4)MIICl2(1-6; M = Mn, Fe, Co; R = tBu, Me), were synthesized to enable a systematic comparison of metal-dependent structural, redox, and catalytic properties within a unified N4 coordination environment. Single-crystal X-ray structures showed consistent octahedral geometries of the series, with axial M-N elongation modulated by ligand sterics and metal identity. Cyclic voltammetry and DFT calculations revealed metal-centered oxidations and ligand-centered reductions, the latter exhibiting pronounced dependence on both the ligand and the metal, with increasingly accessible reduction potentials from Mn to Co. One-electron oxidation yielded MIII derivatives 1+-3+, whose structural and magnetic parameters confirmed high-spin MnIII and FeIII, but a low-spin CoIII state for 3⁺. The catalytic reactivity of 1-6 and 1⁺-3⁺ was evaluated in C(sp2)-C(sp2) Kumada cross-coupling of aryl bromides with PhMgCl. Co complexes displayed the highest activity, whereas Mn and Fe complexes were inactive or poorly selective. Cross-coupling yields correlated strongly with E1/2,red, indicating that access to low-valent MI intermediates is essential for productive catalysis. These results establish pyridinophane ligands as a powerful framework for isolating metal-dependent reactivity trends and provide insight into the distinct catalytic behavior of Mn, Fe, and Co complexes under identical ligand environments.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149152775","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":"Next-Generation Supercapacitors: Integrating Advanced Materials, Emerging Functionalities, and Machine Learning","authors":"Kaustubh Kumbhar,Tajala Magray,Mahboobeh Shahbazi,Pradip Bhikaji Sarawade,Brahim Aissa,Dattatray Sadashiv Dhawale","doi":"10.1039/d6qi01806h","DOIUrl":"https://doi.org/10.1039/d6qi01806h","url":null,"abstract":"This review addresses these limitations and proposes forward-looking strategies based on rational material design, interpretable machine learning frameworks, comprehensive regulatory guidelines, and circular manufacturing practices to chart a path toward sustainable, intelligent, and multifunctional supercapacitors that can smoothly integrate into future technologies while supporting an environmentally responsible energy landscape.The rapid evolution in energy storage technologies has placed supercapacitors (SCs) at the heart of next-generation applications. SCs bridge the gap between traditional capacitors and batteries due to their fast-charging capability, high power output, and long cycle life. New developments have inspired novel directions in material design, electrode architecture, and hybrid configurations. These involve new trends such as flexible, stretchable, biodegradable, and edible supercapacitors, as well as electrochromic and even self-healing systems with previously unattainable energy and power densities. New materials, including conductive hydrogels, MXenes, biopolymers, and hybrid nanocomposites, drove the development of novel functionalities. These have resolved some of the existing challenges in wearable electronics, sustainable energy storage, and, especially, biomedical implants. These materials exhibit excellent electrochemical performance combined with high mechanical flexibility. Meanwhile, the integration of machine learning (ML) into supercapacitor-related research is revolutionizing materials science through rapid material discovery, optimized fabrication procedures, and the prediction of device performance with unprecedented accuracy. ML-based frameworks also enable real-time health monitoring, lifetime prediction, and automated device design, with significantly fewer experimental cycles. The convergence of these innovative material trends, together with multifunctional capabilities and ML-driven methodologies, propels next-generation supercapacitors toward intelligent, adaptive, and application-specific energy systems. Even so, several major challenges remain and need to be addressed, including achieving long-term stability, improving biocompatibility, developing enhanced characterization techniques, and implementing scalable manufacturing processes. This review addresses these limitations and proposes forward-looking strategies based on rational material design, interpretable machine learning frameworks, comprehensive regulatory guidelines, and circular manufacturing practices to chart a path toward sustainable, intelligent, and multifunctional supercapacitors that can smoothly integrate into future technologies while supporting an environmentally responsible energy landscape","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"238 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151991","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":"Formulating low-cost β-type intergrowth sodium manganese-based layered oxide cathodes: competitive phase regulation, stabilized bulk/interfacial chemistry, and suppressed Jahn–Teller distortion","authors":"Haiyan Li,Yifeng Liu,Yameng Fan,Haiyan Hu,Yaping Yan,Xinyu Liu,Hanshen Xin,Wentao Wu,Yanfang Zhu,Shun Wang,Yao Xiao","doi":"10.1039/d6qi01709f","DOIUrl":"https://doi.org/10.1039/d6qi01709f","url":null,"abstract":"Manganese-based layered oxides are promising cathode materials for low-cost sodium-ion batteries, but their electrochemical performance is often limited by complex multiphase evolution, Mn3+-driven Jahn–Teller distortion, and sluggish Na+ transport. Herein, Na0.9MnO2 is selected as a model system to develop a Cu/Ti co-substitution strategy for phase-competition engineering. Cu preferentially promotes β-phase formation, whereas Cu/Ti suppresses Jahn–Teller distortion and stabilizes the local MnO6 coordination environment, cooperatively directing the phase assemblage toward a coherent β/P2 intergrowth structure. Structural and spectroscopic analyses reveal reduced lattice distortion, alleviated depth-dependent Mn valence heterogeneity, improved local coordination reversibility, and the formation of a compositionally graded cathode–electrolyte interphase, collectively mitigating bulk and interfacial degradation. Benefiting from this coupled bulk–interface regulation, Na0.9Mn0.90Cu0.05Ti0.05O2 delivers discharge capacities of 163.55 mAh g−1 at 0.1 C and 97.79 mAh g−1 at 2 C over 1.8–4.3 V, demonstrating enhanced Na+ storage kinetics. A non-presodiated full cell further achieves an initial discharge capacity of 96.47 mAh g−1 at 0.1 C over 1.5–4.2 V, providing preliminary validation of its practical feasibility. This work establishes hetero-cation-induced phase-competition engineering as an effective approach for simultaneously regulating phase evolution, lattice distortion, Na+ transport, and interfacial chemistry in low-cost manganese-based layered oxide cathodes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"29 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151992","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":"Carboxyl-Group-Anchored Structural Polarity in a Layered Metal Halide for High-Performance Self-Powered X-ray Detection","authors":"Chengke Fu,Huang Ye,Junhua Luo,Hang Li,Lijun Xu,Chengshu Zhang,Yao Li,Mutong Geng,Qianwen Guan,Ji Qi","doi":"10.1039/d6qi02100j","DOIUrl":"https://doi.org/10.1039/d6qi02100j","url":null,"abstract":"Polar metal halide perovskites that exhibit the bulk photovoltaic effect (BPVE) are promising candidates for self-powered X-ray detection because they can generate photoresponses at zero bias. However, typical interlayer noncovalent interactions often suffer from limited directionality and weak anchoring capability, which hinders the simultaneous construction of polar structures and enhancement of lattice stability. Herein, we develop a carboxyl-substitution strategy to construct a polar two-dimensional (8-AOC) 2 PbBr 4 (8-AOC = 8-aminocaprylic acid) perovskite, thereby achieving efficient and durable self-powered X-ray detection. Carboxyl substitution is accompanied by inorganic-framework distortion within the polar P2 1 space group and by a cross-linked interlayer hydrogen-bonding network that inhibits ion migration. Consequently, the detector achieves a high sensitivity of 128.08 μC Gy -1 cm -2 and a LoD of 98.8 nGy s -1 at zero bias, approximately 1/56 of the conventional medical diagnostic dose rate threshold (5.5 μGy s -1 ). Notably, the device retains 95.9% of its initial sensitivity after 30 days of ambient storage and delivers stable responses during repeated X-ray irradiation, demonstrating strong storage and irradiation-cycling stability. This work presents carboxyl-group functionalization as a strategy for combining polar-structure design with interlayer hydrogen-bond stabilization in self-powered X-ray detectors.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"12 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151990","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":"Equatorial thiolate ligand effects in polynuclear dysprosium metallocene single-molecule magnets.","authors":"Dan Liu, Abdullah A Al-Kahtani, Liviu Chibotaru, Dinh Cao Huan Do, Fu-Sheng Guo, Richard A Layfield","doi":"10.1039/d6qi01594h","DOIUrl":"10.1039/d6qi01594h","url":null,"abstract":"<p><p>Thiolate ligands provide a valuable platform on which to study how soft, polarizable donor atoms affect local magnetic anisotropy and exchange coupling in polynuclear dysprosium single-molecule magnets (SMMs). Here, we report the synthesis of the naphthylthiolate-bridged dysprosium metallocene dimer [(Cp^Me)₂Dy(μ-SNaph)]₂ (Dy₂S₂) and trimer [(Cp^Me)₂Dy(μ-SNaph)]₃ (Dy₃S₃) (Cp^Me = C₅H₄Me), obtained selectively through temperature-dependent crystallization from the same reaction mixture. The two compounds enable direct comparison of the influence of nuclearity on magnetic behaviour while retaining closely related dysprosium coordination environments. Both compounds exhibit zero-field SMM behaviour with similar effective barriers to magnetic relaxation of 61 and 64 cm^-1, respectively, together with significant Raman relaxation at lower temperatures. <i>Ab initio</i> calculations reveal strongly axial ground Kramers doublets with comparable crystal field splittings for all Dy³⁺ centres. The calculations accurately reproduce the experimental magnetic susceptibility and isothermal magnetization, revealing that increased nuclearity strengthens the antiferromagnetic exchange without significantly perturbing the local magnetic anisotropy.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" ","pages":""},"PeriodicalIF":6.2,"publicationDate":"2026-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13644314/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149134364","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}