European Journal of Inorganic Chemistry最新文献_第3页

1,3-Bis(tetrylene)s: Emerging Platforms for Functional Main-Group Molecules 1,3-二（四烯）s：功能主基分子的新兴平台

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-28 Epub Date: 2026-08-30 DOI: 10.1002/ejic.70309

Daichi Uchida, Yoshiyuki Mizuhata

{"title":"1,3-Bis(tetrylene)s: Emerging Platforms for Functional Main-Group Molecules","authors":"Daichi Uchida, Yoshiyuki Mizuhata","doi":"10.1002/ejic.70309","DOIUrl":"https://doi.org/10.1002/ejic.70309","url":null,"abstract":"Main-group chemistry has undergone a resurgence as chemists seek reactivity patterns that do not rely on transition metals. Among low-valent main-group compounds, tetrylenes (R2E:, E = Si, Ge, Sn, Pb) occupy a central position because their ambiphilic electronic structures enable diverse bond activation and coordination chemistry. Although adjacent low-valent Group 14 systems, including 1,2-bis(tetrylene)s, ditetrynes, and related heavier alkyne-type compounds, have been widely investigated as cooperative platforms, 1,3-bis(tetrylene)s remain comparatively underexplored. In this review, we summarize recent developments in 1,3-bis(tetrylene) chemistry, with emphasis on synthesis, structure, electronic properties, and reactivity. The discussion is organized according to the identity of the bridging atom, covering systems bridged by pnictogen, chalcogen, and tetrel (Group 14) elements. By comparing these bridge motifs, we highlight how electronic stabilization, steric protection, and geometric constraint govern the balance between stability and reactivity. Finally, we discuss future opportunities for using 1,3-bis(tetrylene)s as cooperative main-group platforms for bond activation, ligand design, catalysis, and the construction of heavy-element π systems.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 28","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.70309","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149068420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Hydrolysis and Coordination of Zr(IV) in Sulfuric Acid: Radiation Effects and Coassembly With Uranyl Zr（IV）在硫酸中的水解与配位：辐射效应及与铀酰的共聚

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-28 Epub Date: 2026-08-26 DOI: 10.1002/ejic.70310

Junyi Li, Yifei Dang, Ying Jiang, Junren Wang, Xintong Guo, Boyang Song, Penglin Dou, Hailong Zhang, Kai Li, Siyan Huang, Jianrong Zeng, Kecheng Cao, Shuao Wang, Yaxing Wang

{"title":"Hydrolysis and Coordination of Zr(IV) in Sulfuric Acid: Radiation Effects and Coassembly With Uranyl","authors":"Junyi Li, Yifei Dang, Ying Jiang, Junren Wang, Xintong Guo, Boyang Song, Penglin Dou, Hailong Zhang, Kai Li, Siyan Huang, Jianrong Zeng, Kecheng Cao, Shuao Wang, Yaxing Wang","doi":"10.1002/ejic.70310","DOIUrl":"https://doi.org/10.1002/ejic.70310","url":null,"abstract":"Zirconium, a key component of nuclear fuel cladding materials, is commonly present in highly acidic aqueous environments associated with nuclear fuel processing and radioactive waste systems. Although Zr(IV) hydrolysis has been extensively studied, its behavior under radiolytic and actinide-containing acidic conditions remains poorly understood. Here, we investigate the hydrolysis and coordination chemistry of Zr(IV) in 2 M H2SO4 both in the absence and in the presence of γ-radiation and U(VI). In 2 M H2SO4, Zr(IV) forms amorphous Zr(IV)–SO42−–OH aggregate driven by sulfate coordination. γ-Irradiation reduces aggregate size without significantly altering the local Zr coordination environment, as confirmed by transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS) measurements. Under electron-beam irradiation during TEM imaging, these aggregates undergo decomposition followed by crystallization. In situ electron-beam mass spectrometry indicates that radiolysis of aqueous components promotes atomic rearrangement and generates a localized reducing environment, leading to ZrS2 formation. The presence of U(VI) alters the Zr(IV) coordination environment and inhibits Zr(IV)–SO42−–OH aggregates formation. Upon γ-irradiation of mixed Zr(IV)/U(VI) solutions, cubic-shaped amorphous U(VI)–Zr(IV)–SO42−–OH assemblies are formed, likely through OH•-mediated coordination and aggregation processes. These findings provide new insights into the coordination chemistry and radiolytic aggregation behavior of Zr(IV) in highly acidic actinide-containing environments.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 28","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149068082","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Redox Halido-Based Reactivity on the Addition of Bromine to Linear NHC Gold Halides 线性NHC金卤化物中溴的氧化还原反应性

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-28 Epub Date: 2026-09-09 DOI: 10.1002/ejic.70315

Nicola Sargentoni, Rossana Galassi, Lorenzo Luciani, Gabriele Manca, Andrea Ienco

{"title":"Redox Halido-Based Reactivity on the Addition of Bromine to Linear NHC Gold Halides","authors":"Nicola Sargentoni, Rossana Galassi, Lorenzo Luciani, Gabriele Manca, Andrea Ienco","doi":"10.1002/ejic.70315","DOIUrl":"https://doi.org/10.1002/ejic.70315","url":null,"abstract":"Halogen addition to a linear gold complex to form a square-planar species is one of the most representative examples of what is generally classified as an “oxidative addition” process. This work examines the addition of bromine to the linear complexes labeled as NHCMe, BnAuX (with NHCMe, BnAuX indicating complexes obtained both with 1,3-dimethylimidazol-2-yl and 1-benzyl-3-dimethylimidazol-2-yl and X = Cl or I), which generally yield heterohalide square-planar gold derivatives. The products have been confirmed by X-ray structural characterization, highlighting the possibility of isomerism and the key role of both the halogen atom and the substituents on the carbene ligand in favoring the formation of one product over another. From this perspective, a distinctive reactivity emerges, revealing the possibility of obtaining homohalide derivatives containing three bromide ligands under different experimental conditions, depending on the nature of the halide in the initial linear complex. This reactivity implies a redox process with an electron transfer between the halide ligand and a Br2 molecule. Detailed DFT calculations reveal the occurrence of the inverted ligand field for all square-planar products and intermediates. The analysis, also supported by Raman experiments, shows that the homohalide derivatives can form via halogen-bonded intermediates, accompanied by the elimination of IBr or BrCl moieties.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 28","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149068348","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Synthesis of Zwitterionic Tris(pyrazolyl) Ligands and Their Mn(II) Bis-Chelates Exhibiting Charge–Transfer-Induced Spin Crossover 具有电荷转移诱导自旋交叉的两性离子三（吡唑）配体及其Mn（II）双螯合物的合成

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-28 Epub Date: 2026-08-31 DOI: 10.1002/ejic.70314

Matthew C. Kessinger, Tzu-Ching Cheng, Cameron Brillhart, Sreenivasulu Chinnabattigalla, Carla Slebodnick, Amanda J. Morris

{"title":"Synthesis of Zwitterionic Tris(pyrazolyl) Ligands and Their Mn(II) Bis-Chelates Exhibiting Charge–Transfer-Induced Spin Crossover","authors":"Matthew C. Kessinger, Tzu-Ching Cheng, Cameron Brillhart, Sreenivasulu Chinnabattigalla, Carla Slebodnick, Amanda J. Morris","doi":"10.1002/ejic.70314","DOIUrl":"https://doi.org/10.1002/ejic.70314","url":null,"abstract":"Hydro-tris(pyrazolyl)borate-based scorpionates are cornerstone ligands in coordination chemistry, offering precise control over the steric and electronic environment of metal centers. In contrast, their emerging zwitterionic analogs remain largely unexplored. With intermediate ligand donor strength, these ligands provide a distinctive handle for fine-tuning the electronic structures of metal complexes. Expanding this nascent class opens new avenues for probing fundamental processes in coordination chemistry. In the present study, the synthesis and characterization of new zwitterionic scorpionates with the general formula [base]+-[B–Pz3]− are presented. In addition, a synthetic procedure for preparing their bis-chelates with divalent manganese ions is provided; this topic remains largely unexplored. Systematic modification of the zwitterionic ligand series (1a–1f) allows precise fine-tuning of their sigma-donor strength, establishing a direct correlation with the Mn(II/III) oxidation potentials determined by cyclic voltammetry. These complexes and their chemically oxidized counterparts are characterized using single-crystal, magnetic, and electrochemical techniques to study the charge–transfer-induced spin crossover inherent to this class of compounds.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 28","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.70314","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149068549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Ligand Redox Noninnocence in Bis(phosphinimine) Diarylamido Pincer Complexes of Nickel 镍的二（膦亚胺）二芳胺螯合物的配体氧化还原非无罪性

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-28 Epub Date: 2026-08-26 DOI: 10.1002/ejic.70312

Xiujing Xing, Ryan P. Murphy, David P. Hales, Qiuran Wang, Ariana Z. Spentzos, Laura M. Thierer, Michael R. Gau, Patrick J. Carroll, Neil C. Tomson

{"title":"Ligand Redox Noninnocence in Bis(phosphinimine) Diarylamido Pincer Complexes of Nickel","authors":"Xiujing Xing, Ryan P. Murphy, David P. Hales, Qiuran Wang, Ariana Z. Spentzos, Laura M. Thierer, Michael R. Gau, Patrick J. Carroll, Neil C. Tomson","doi":"10.1002/ejic.70312","DOIUrl":"https://doi.org/10.1002/ejic.70312","url":null,"abstract":"A series of Ni(II) complexes were generated through ligation by a chelating diarylamido ligand bearing diphenylmethylphosphinimine-based donors in the ortho positions of the aryl groups: HN[2-(NPPh2Me)-4-R-C6H3]2 (RH, Me). This ligand displays both chemical and redox noninnocence, including the generation of a rare, metal-bound aminyl radical. Several four- or five-coordinate Ni(II) complexes of various geometries were obtained, including chloride, phenoxide, and metallacyclic complexes, the latter of which result from ligand activation. Cyclic voltammetry (CV) of the four-coordinate complexes showed reversible oxidation events (E1/2 = ca. –0.5 V vs. Fc0/+) and the oxidation product of the phenoxide complex was fully characterized. The oxidation was determined to be primarily ligand-centered, as supported by electron paramagnetic resonance spectroscopy, X-ray crystallography, and density functional theory (DFT) calculations. More anodic, irreversible oxidation features were also observed for these complexes by CV (Ean = ca. +0.1 V vs. Fc0/+). DFT computations on the second oxidation were consistent with a second ligand-centered process to generate nitrenium-like (R2N+) electronic structures. These studies showcase the versatility of this pincer ligand both by stabilizing complexes of varying geometries and coordination numbers and by providing electrons during oxidation.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 28","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.70312","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149068083","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Metal Nanoclusters as Catalysts for Organoborane Synthesis: Recent Advances and Mechanistic Insights 金属纳米团簇作为有机硼烷合成的催化剂：最新进展和机理见解

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-28 Epub Date: 2026-08-21 DOI: 10.1002/ejic.70308

Bhargav Prakash, Aishwarya Prakash, Srinivasa Budagumpi, Shubhankar Kumar Bose

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Hydrostatic and Anisotropic Pressure Responses in Tetragonal Zirconia Nanoparticles 四边形氧化锆纳米颗粒的流体静力和各向异性压力响应

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-20 Epub Date: 2026-08-31 DOI: 10.1002/ejic.70302

Yuki Konno, Natsuki Asano, Ai Amatatsu, Kenta Imoto, Shin-ichi Ohkoshi, Hiroko Tokoro

{"title":"Hydrostatic and Anisotropic Pressure Responses in Tetragonal Zirconia Nanoparticles","authors":"Yuki Konno, Natsuki Asano, Ai Amatatsu, Kenta Imoto, Shin-ichi Ohkoshi, Hiroko Tokoro","doi":"10.1002/ejic.70302","DOIUrl":"https://doi.org/10.1002/ejic.70302","url":null,"abstract":"Tetragonal zirconia is a metastable phase that is typically hidden at room temperature but becomes observable when the particle size is reduced to the nanoscale. Unlike typical phase transition materials, zirconia exhibits an unusual thermodynamic relationship in which the metastable tetragonal phase possesses a smaller volume than the thermodynamically stable monoclinic phase. In this study, we investigate the pressure-induced phase transition behavior of tetragonal zirconia nanoparticles under hydrostatic and anisotropic pressure conditions. Tetragonal zirconia nanoparticles were synthesized and subjected to anisotropic and hydrostatic pressure. X-ray diffraction measurements reveal that the tetragonal phase remains largely stable even under hydrostatic pressure up to ~1000 MPa. Conversely, anisotropic pressure readily induces a tetragonal-to-monoclinic transformation. Under strong anisotropic pressure, approximately half of the phase transforms to the monoclinic phase at pressures as low as ~50 MPa, indicating a high sensitivity to nonhydrostatic stress components. This pressure-response behavior is interpreted by considering the isotropic stress generated under hydrostatic pressure and the local strain arising from the inhomogeneous stress distribution under anisotropic loading. These findings indicate that tetragonal zirconia nanoparticles can serve as sensitive probes for detecting nonhydrostatic pressure components in the MPa range, thus providing an approach for evaluating pressure anisotropy under practical pressure environments.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 27","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.70302","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149007422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

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Surrogate-Guided Latent-Space Reinforcement Learning for Generative Ligand Design in Am(III)/Eu(III) Separation Am(III)/Eu（III）分离中生成配体设计的代理引导潜在空间强化学习

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-20 Epub Date: 2026-08-13 DOI: 10.1002/ejic.70304

Haorui Li, Yulong Que, Dongsheng Yang, Zhisong Bao, Yihuang Wu, Zhiyuan Zhang, Chong Liu

{"title":"Surrogate-Guided Latent-Space Reinforcement Learning for Generative Ligand Design in Am(III)/Eu(III) Separation","authors":"Haorui Li, Yulong Que, Dongsheng Yang, Zhisong Bao, Yihuang Wu, Zhiyuan Zhang, Chong Liu","doi":"10.1002/ejic.70304","DOIUrl":"https://doi.org/10.1002/ejic.70304","url":null,"abstract":"Am(III)/Eu(III) separation is a stringent benchmark for actinide/lanthanide partitioning because the two trivalent ions exhibit closely related size and solution chemistry, making selectivity highly dependent on subtle ligand-controlled coordination differences. Herein, we report a surrogate-guided latent-space reinforcement learning workflow for generative ligand design under sparse and heterogeneous extraction-data conditions. A junction-tree variational autoencoder was pretrained on ligand structures extracted from CSD-derived coordination compounds and fine-tuned on literature-reported Am/Eu extractants to construct a chemically valid ligand latent space. A condition-aware XGBoost surrogate model predicted ln(SF) from ligand, solvent, and experimental-condition features and supplied the reward signal for proximal policy optimization (PPO). The surrogate retained useful ranking ability, including under a strict ligand-level split, while PPO enriched multiple regions associated with high surrogate-predicted performance. The generated candidates recapitulated established soft-donor and N-heterocyclic design patterns while suggesting new structural variants in the learned ligand space. This workflow demonstrates how surrogate-guided generative optimization can translate limited Am/Eu extraction data into chemically meaningful ligand-design hypotheses.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 27","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149007541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

p-Block Initiator/Ylide Systems for the Polyhomologation Reaction: Computational Benchmarking of Group III Organoinitiators and Ylides Versus Trihexylborane/Corey’s Ylide 多同源反应的p-嵌段引发剂/Ylide体系：III族有机引发剂和Ylide与三己基硼烷/Corey Ylide的计算基准

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-20 Epub Date: 2026-08-16 DOI: 10.1002/ejic.70305

Darien I. Martínez-Valencia, Gerardo González-García, Francisco J. Tenorio, J. Oscar C. Jiménez-Halla, J. Armando Luján-Montelongo, José E. Báez

{"title":"p-Block Initiator/Ylide Systems for the Polyhomologation Reaction: Computational Benchmarking of Group III Organoinitiators and Ylides Versus Trihexylborane/Corey’s Ylide","authors":"Darien I. Martínez-Valencia, Gerardo González-García, Francisco J. Tenorio, J. Oscar C. Jiménez-Halla, J. Armando Luján-Montelongo, José E. Báez","doi":"10.1002/ejic.70305","DOIUrl":"https://doi.org/10.1002/ejic.70305","url":null,"abstract":"We computationally investigate the initiation step in polyhomologation (PH) and evaluate the reaction mechanisms of multiple initiator/ylide combinations with the aim of expanding the scope of traditional PH while preserving its key advantages. All energy profiles were benchmarked against the well-established trihexylborane/dimethylsulfoxonium methylide (Corey’s ylide) system. Our model set comprises tripropylborane, -alane, and -galane initiators paired with nitrogen- and phosphorus-based methylides. The tripropylborane/trimethylammonium methylide mechanism closely corresponds to the reference pathway, and diazonium methylide in combination with tripropylborane, tripropylalane, or tripropylgalane also reproduces the characteristic features of the established PH reaction pathway, with 1,2-migration barriers ranging from 16.9 to 24.8 kcal mol−1. These results indicate that such initiator/ylide pairs constitute experimentally viable candidates for extending PH chemistry. Across all systems, nitrogen-derived ylides consistently promote PH initiation more efficiently than their phosphorus analogs, primarily due to the lower strain associated with the structural deformation of the ylide fragment and the different rigidity imposed by its substituents. Together, these mechanistic trends provide a coherent picture of initiation in PH and, supported by complementary computational analyses, offer an initial framework that can guide future development of new p-block-based initiator/ylide systems.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 27","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149007395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Synthesis and Electrocatalytic Hydrogen Evolution Performance of Ruthenium Complexes Constructed With Terpyridine Carboxylic Acid 三元吡啶羧酸钌配合物的合成及其电催化析氢性能

IF 1.8 4区化学

European Journal of Inorganic Chemistry Pub Date : 2026-09-20 Epub Date: 2026-08-21 DOI: 10.1002/ejic.70301

Yuhang Huang, Jie Yi, Shiyu Xiao, Manbo Zhang, Tianlü Xu, Ruixiang Hu

{"title":"Synthesis and Electrocatalytic Hydrogen Evolution Performance of Ruthenium Complexes Constructed With Terpyridine Carboxylic Acid","authors":"Yuhang Huang, Jie Yi, Shiyu Xiao, Manbo Zhang, Tianlü Xu, Ruixiang Hu","doi":"10.1002/ejic.70301","DOIUrl":"https://doi.org/10.1002/ejic.70301","url":null,"abstract":"Three novel ruthenium complexes (Ru1–Ru3) were synthesized from RuCl3, terpyridine carboxylic acid, and auxiliary ligands PPh3, DPPPy, or H2dcbpy, and characterized by single-crystal X-ray diffraction (SC-XRD), elemental analysis (EA), infrared spectroscopy (IR), and ultraviolet-visible (UV–vis) spectroscopy. The hydrogen evolution reaction (HER) performance of Ru1 and Ru2 was evaluated in alkaline, neutral, and acidic electrolytes. Ru2 exhibited the best activity in 1.0 mol L−1 KOH, with an ECSA of 47.5, η10 of 380 mV, Tafel slope of 375.6 mV dec−1, and turnover frequency (TOF) of 97.7 h−1 at 475.6 mV overpotential. Density functional theory calculations revealed that the DPPPy ligand in Ru2 narrows the gap between the highest occupied molecular orbital (HOMO) and lowest unoccupied orbital (LUMO) (2.90 vs. 3.21 eV), raises the HOMO level (−5.28 vs. −8.22 eV), and increases the positive charge on Ru (+0.173 vs. +0.063), thereby promoting electron transfer and hydride formation. This work demonstrates that ligand engineering provides a rational strategy for designing efficient molecular ruthenium electrocatalysts for hydrogen evolution.","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"29 27","pages":""},"PeriodicalIF":1.8,"publicationDate":"2026-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149007543","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0