Inorganic Chemistry最新文献_第3页

Bond-Level Prediction of U-Donor Bond Lengths in Uranyl Coordination Complexes Using Machine Learning for Ligand Recognition 用机器学习进行配体识别的铀酰配位配合物u -供体键长预测

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-08 DOI: 10.1021/acs.inorgchem.6c03025

Mingyu Liu, Tongtong Sun, Tianchen Wang, Chunyuan Zhan, Bo Liang, Yu Su, Jingyang Wang, Yu Zhou, Chunhui Li, Yitung Chen, Tingting Liu, Wentao Wang, Taihong Yan, Meng Zhang

{"title":"Bond-Level Prediction of U-Donor Bond Lengths in Uranyl Coordination Complexes Using Machine Learning for Ligand Recognition","authors":"Mingyu Liu, Tongtong Sun, Tianchen Wang, Chunyuan Zhan, Bo Liang, Yu Su, Jingyang Wang, Yu Zhou, Chunhui Li, Yitung Chen, Tingting Liu, Wentao Wang, Taihong Yan, Meng Zhang","doi":"10.1021/acs.inorgchem.6c03025","DOIUrl":"10.1021/acs.inorgchem.6c03025","url":null,"abstract":"U-donor bond lengths in uranyl coordination complexesdirectlyreflect metal–ligand interaction strength and provide importantstructural parameters for evaluating ligand recognition, selectivecomplexation, and extraction/adsorption system design. To enable bond-levelprediction, this study developed a DFT-derived machine learning frameworkfor predicting U-donor bond lengths. A data set containing 15,177coordination structures and 26,798 U-donor bond length data pointswas constructed from 3,330 unique ligands under a unified computationalprotocol. Five categories of models, including linear models, support-vector-basedmodels, ensemble tree models, descriptor-based neural networks, andgraph neural networks, were evaluated to compare representation strategies.Among descriptor-based models, XGBoost achieved the best performance,with R2, RMSE, and MAE values of 0.793,0.057 Å, and 0.039 Å, respectively. Among graph neural networks,DimeNet++ performed best, with R2, RMSE,and MAE values of 0.821, 0.051 Å, and 0.036 Å. Functional-group-basedevaluation and SHAP analysis indicated that donor atom type, neighboringatomic environment, local electronegativity difference, and localgeometric features are key factors controlling U-donor bond lengthvariations. External validation using unseen functional groups anduranyl structures demonstrated model generalization beyond the trainingspace. This work provides a bond-level data set and a data-drivenstrategy for rapid U-donor bond length prediction and ligand screeningin actinide coordination systems.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24183–24196"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149151098","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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Cyano-Engineered Tetraphenylethene-Based Pd2L4 Metallacages for Iodide Detection 氰化工程四苯乙烯基Pd2L4金属材料用于碘化物检测

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-07 DOI: 10.1021/acs.inorgchem.6c04441

Ao Yang, Rui Cao, Wenxi Li, Beibei Li, Yuan-Qing Xu, Yibo Zhao, Youzhi Xu

引用次数: 0

Synthesis and Photothermal Properties of Mn(III) Complexes with Carbazole-Bridged Bis-NHC Ligands 咔唑桥接双- nhc配体Mn（III）配合物的合成及光热性质

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-08 DOI: 10.1021/acs.inorgchem.6c03223

Pangang Du, Xianda Wu, Jianbin Chen, Lei Gong, Yu-Mei Lin

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Ligand Local Rigidity as a Quantitative Descriptor of Lanthanide Size Selectivity 配体局部刚性作为镧系元素尺寸选择性的定量描述符

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 DOI: 10.1021/acs.inorgchem.6c05141

Anton S. Pozdeev,Santa Jansone-Popova,De-en Jiang

{"title":"Ligand Local Rigidity as a Quantitative Descriptor of Lanthanide Size Selectivity","authors":"Anton S. Pozdeev,Santa Jansone-Popova,De-en Jiang","doi":"10.1021/acs.inorgchem.6c05141","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c05141","url":null,"abstract":"Separation of the rare-earth elements relies on the small, monotonic contraction in the ionic radius across the trivalent lanthanide series. Ligand preorganization is a powerful strategy for amplifying this size difference, but within the N,O-tetradentate ligand family examined here, it approaches a structural ceiling as the most preorganized scaffolds become fully fused. Here, using density functional theory, we introduce cavity rigidity as a quantitative framework for lanthanide size selectivity and define local rigidity (LR) as the resistance of the ligand cavity to the compression required for metal binding. The LR reflects both the intrinsic stiffness of the ligand framework and the extent to which the cavity must deform upon coordination. Across the N,O-tetradentate ligands examined, the computed La/Lu size selectivity increases linearly with LR. The same relationship is observed for five additional lanthanide pairs with larger ionic radius differences producing steeper slopes. Within this ligand family, the results point to two routes for increasing thermodynamic size selectivity: increasing the framework stiffness or increasing the equilibrium donor separation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210891","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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Ditopic Bis(Pyridinium Amidate) Ligands with N,N- and O,O-Bidentate Bonding Sites: Oxygen-Coordinated Alkali Metals Systematically Impact the Reactivity of the N-Bound Palladium Center 具有N，N-和O，O-双齿键位的双位双（酰胺吡啶）配体：氧配位碱金属系统地影响N键钯中心的反应性

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 DOI: 10.1021/acs.inorgchem.6c03207

Esaïe Reusser,Claire J. Benedict,Martin Albrecht

{"title":"Ditopic Bis(Pyridinium Amidate) Ligands with N,N- and O,O-Bidentate Bonding Sites: Oxygen-Coordinated Alkali Metals Systematically Impact the Reactivity of the N-Bound Palladium Center","authors":"Esaïe Reusser,Claire J. Benedict,Martin Albrecht","doi":"10.1021/acs.inorgchem.6c03207","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03207","url":null,"abstract":"Alkali metal (AM) salts are widely used as bases or additives in homogeneous catalysis, yet the influence of the AM cation itself is often overlooked. Here, we demonstrate that AM binding to the backbone of a bis(pyridinium amidate) (bisPYA) ligand affects the reactivity of the coordinated palladium center. Specifically the ortho-pyridinium bisPYA ligand adopts an N,N′-bidentate bonding mode to PdX2 fragments with X = MeCN(BF)4 (3), Cl (4), or OAc (5). When exposed to AM carbonates, the dicarbonyl backbone of the bis(amidate) ligand coordinates in an O,O′-bidentate fashion to the AM to form stable and crystalline complexes of the type [AM(bisPYA-PdOAc2)2]+ with AM = Li (6a), Na (6b), K (6c), Rb (6d), and Cs (6e). The stability of these AM adducts decreases according to competitive binding and dilution experiments along the series Li+ > Na+ > K+ > Rb+ > Cs+. In agreement with this trend, rates of electrophilic cyclometalation involving C–H bond activation of the pyridinium N–CH3 group correlate with the stability of the adducts, thus providing valuable insights relevant to understanding specific AM effects in transition metal catalysis and offering opportunities to remotely tune the electron density of catalytic centers in this bisPYA and related ligand classes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218792","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Impact of the Metal–Ligand Bonding Nature on Electronic States of {Fe(NO)2}9/10–{Fe(NO)2}9/10 RREs Unraveled by the Combined X-ray Spectroscopic Analyses: Relevance to DNIC-Mediated Translational Functionality 金属-配体结合性质对{Fe(NO)2}9/10 - {Fe(NO)2}9/10 RREs电子态的影响：与dnic介导的翻译功能相关

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 DOI: 10.1021/acs.inorgchem.6c03317

Sen-Hung Hsieh,Jia-Yu Lin,Feng-Tian Chang,Chi-Yen Tung,Nozomu Hiraoka,Shu-Chih Haw,Fu-Te Tsai,I-Jui Hsu,Wen-Feng Liaw

{"title":"Impact of the Metal–Ligand Bonding Nature on Electronic States of {Fe(NO)2}9/10–{Fe(NO)2}9/10 RREs Unraveled by the Combined X-ray Spectroscopic Analyses: Relevance to DNIC-Mediated Translational Functionality","authors":"Sen-Hung Hsieh,Jia-Yu Lin,Feng-Tian Chang,Chi-Yen Tung,Nozomu Hiraoka,Shu-Chih Haw,Fu-Te Tsai,I-Jui Hsu,Wen-Feng Liaw","doi":"10.1021/acs.inorgchem.6c03317","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03317","url":null,"abstract":"Probed by the combined X-ray spectroscopic techniques (N K-edge/Fe L-edge XAS, Fe K-edge HERFD–XANES, Kβ1,3 mainline, VtC Kβ2,5 XES) and DFT computation, the qualitative/quantitative assignment of Fe/NO oxidation states in dinuclear dinitrosyl iron complexes (DNICs) suggests that the balance between NO– → Fe π-donating and Fe → •NO π-backbonding interactions in the [Fe(NO)2] unit(s) is modulated by the ionicity-covalency competition within the Fe–ER(2) bonds for a series of [ER(2)]−-bridged {Fe(NO)2}9/10–{Fe(NO)2}9/10 RREs (E = S, N, O). With the delicately ligand-controlled NO–/•NO equilibrium in the [Fe(NO)2] unit, the biomimetic activity governed by {Fe(NO)2}9/{Fe(NO)2}10 DNICs echoes their electronic/spectroscopic features, which not only uncovers molecular identity in complex environments but also decodes the reported H2S/NO communication, degradation/repair of [Fe–S] clusters, and translational functionality for NO-to-[N2O2]2–-to-N2O and NO-to-HNO/NO– transformations.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218795","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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

Cyclopentadienyl in Cp2Hf Complexes Is No Longer a Spectator Ligand: Reactions of a Hafnacyclocumulene Complex with Ketones Cp2Hf配合物中的环戊二烯不再是一个旁观配体：一种环戊二烯配合物与酮的反应

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 DOI: 10.1021/acs.inorgchem.6c03290

Mikhail A. Frolov,Maxim V. Andreev,Rinat R. Aysin,Elizaveta R. Nurzhanova,Alexander F. Smol’yakov,Vladimir V. Burlakov

{"title":"Cyclopentadienyl in Cp2Hf Complexes Is No Longer a Spectator Ligand: Reactions of a Hafnacyclocumulene Complex with Ketones","authors":"Mikhail A. Frolov,Maxim V. Andreev,Rinat R. Aysin,Elizaveta R. Nurzhanova,Alexander F. Smol’yakov,Vladimir V. Burlakov","doi":"10.1021/acs.inorgchem.6c03290","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.6c03290","url":null,"abstract":"The interaction of five-membered hafnacyclocumulene complex 1Hf with ketones was investigated. The reaction outcome depends on the conditions and the ketone substituents. Under UV irradiation, insertion can be halted at one or two ketone molecules inserted into Hf–C bonds, affording hafnadihydrofuran 2Ph or the nine-membered dioxahafnacyclocumulene 3Fl. Under thermal conditions, the reaction of 1Hf with ketones revealed, for the first time, ketone insertion into one or two Cp–Hf bonds of the metallocene moiety. In the reaction with benzophenone, the corresponding insertion product 4Phb was isolated, and its structure was confirmed by SC-XRD. Products resulting from the insertion of benzophenone or fluorenone into the Cp–Hf bonds of the metallocene fragment of the hafnacyclocumulene were also characterized. A ketone insertion mechanism into the Cp–Hf bonds was proposed based on quantum chemical calculations at the DLPNO–CCSD(T)/Def2-TZVP//r2-SCAN-3c/Def2-TZVP level of theory. The calculation results revealed that the ketone undergoes insertion via η1-type of Cp–Hf bond. Furthermore, benzophenone and fluorenone also insert into the Cp–Hf bonds of hafnocene diphenolates by the same manner. The results obtained allow understanding the general deactivation mechanism in metallocene catalytic processes under interaction with carbonyl compounds.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"56 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218797","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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Hierarchical Heterometallic Coordination Underpins Alkali Tolerance in a Zr–Cu Hydroxamate Framework 层状异金属配位支持Zr-Cu羟基酸酯框架的碱耐受性

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 DOI: 10.1021/acs.inorgchem.6c04358

Xiaoting Li,Chaozhi Xiong,Ziyu Li,Yuxin Liu,Xiangping Duan,Chong Liu

引用次数: 0

Regulating Fe3+ Migration and AlO4-Associated Hydroxyl Evolution via Solid-State Ion Exchange for Enhanced Glycerol Ketalization over Y Zeolite 通过固态离子交换调节fe - 3+迁移和alo4 -相关的羟基演化，以增强沸石上的甘油烷基化

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-02 DOI: 10.1021/acs.inorgchem.6c03793

Renqiang Huang, Le Dou, Yuangao Wang, Yu Luo, Li Xing, Ziqi Zhou, Wei Yu, Zhengxing Qin, Yurou Song, Kongyuan Zhang, Wenjuan Yan, Xin Jin, Chaohe Yang

{"title":"Regulating Fe3+ Migration and AlO4-Associated Hydroxyl Evolution via Solid-State Ion Exchange for Enhanced Glycerol Ketalization over Y Zeolite","authors":"Renqiang Huang, Le Dou, Yuangao Wang, Yu Luo, Li Xing, Ziqi Zhou, Wei Yu, Zhengxing Qin, Yurou Song, Kongyuan Zhang, Wenjuan Yan, Xin Jin, Chaohe Yang","doi":"10.1021/acs.inorgchem.6c03793","DOIUrl":"10.1021/acs.inorgchem.6c03793","url":null,"abstract":"Solid-state ion exchange (SSIE) method generates minimalwastewaterand provides high ion-exchange rates, making it an emerging strategyfor tuning zeolitic structures and properties. However, the mechanisticunderstanding involving ionic diffusion in zeolites remains unclear.In this work, we used Y zeolite as the proof-of-concept case, demonstratingthat FeY catalysts prepared via the SSIE method exhibit superior catalyticactivity for ketalization of glycerol and cyclohexanone. As one ofthe key findings, SSIE induces significantly less structural damageto the zeolite framework than ion exchange in liquid medium, whereFe3+ unusually migrates from supercages to β cagesin the solid state. Na+ species associated with AlO4 tetrahedra are replaced by Fe3+, forming isolatedFe3+ and oligomeric FexOy species that correspond to [Fe(OH)2]+ and [HO-Fe-O-Fe-OH]2+. Consequently, theintroduction of Fe3+ also modulates Lewis acidity, moreimportantly, generating additional Brønsted acid sites. IsolatedFe3+ species are favorably formulated during solid-statediffusion. Computational studies further reveal that the acidic hydroxylgroups associated with isolated Fe3+ species are the intrinsicactive sites for glycerol ketalization. The mechanistic insights provideboth experimental and theoretical foundations for designing next-generationzeolite catalysts for the green synthesis of bio-based specialty chemicals.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24395–24409"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091545","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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Quaternization-Induced Metalloporphyrin-Based Covalent Organic Polymer/MWCNT Hybrid for Bifunctional Water Splitting 季铵化诱导的基于金属卟啉的共价有机聚合物/MWCNT杂化物用于双功能水分解

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2026-10-19 Epub Date: 2026-10-01 DOI: 10.1021/acs.inorgchem.6c03643

Aijian Wang, Pengfei Chen, Jiacheng Hou, Cheng Yuan, Long Zhao, Weihua Zhu, Wei Zhao

{"title":"Quaternization-Induced Metalloporphyrin-Based Covalent Organic Polymer/MWCNT Hybrid for Bifunctional Water Splitting","authors":"Aijian Wang, Pengfei Chen, Jiacheng Hou, Cheng Yuan, Long Zhao, Weihua Zhu, Wei Zhao","doi":"10.1021/acs.inorgchem.6c03643","DOIUrl":"10.1021/acs.inorgchem.6c03643","url":null,"abstract":"Covalent organic polymers (COPs) have attracted considerableattentionas electrocatalysts because of their tunable structures, high porosity,and abundant functional sites, yet their practical application isoften limited by poor electrical conductivity. Herein, conductivemetalloporphyrin-based COP hybrids were synthesized through a quaternization-inducedpolymerization strategy in the presence of multi-walled carbon nanotubes(MWCNTs). The resultant FeTPyPCOP@MWCNTs and NiTPyPCOP@MWCNTs integratemetalloporphyrin coordination sites, a porous polymer framework, anda conductive carbon network within a single architecture. A directcomparison between the two materials reveals that FeTPyPCOP@MWCNTsexhibit superior electrocatalytic activity toward water splitting,highlighting the important influence of the coordinated metal center.FeTPyPCOP@MWCNTs requires overpotentials of only 117 mV for the hydrogenevolution reaction (HER) and 241 mV for the oxygen evolution reaction(OER) at 10 mA cm–2. In a two-electrode electrolyzer,it delivers 10 mA cm–2 at a cell voltage of 1.56V, together with excellent durability and near-quantitative Faradaicefficiency. This work demonstrates that combining metalloporphyrincoordination environments with conductive polymer/carbon architecturesis an effective strategy for developing efficient bifunctional electrocatalystsfor overall water splitting.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"65 41","pages":"24357–24369"},"PeriodicalIF":4.6,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149091597","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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