Applied Organometallic Chemistry最新文献

{"title":"Synthesis of N,N-Dimethylaminoethyl Acrylate via a Zinc Phenoxyimine and Phenoxyamidine Complexes Catalyzed Transesterification Reaction","authors":"Quentin Gaydon,&nbsp;Raluca Malacea-Kabbara,&nbsp;Jérôme Bayardon,&nbsp;Laurent Plasseraud,&nbsp;Michel Picquet,&nbsp;Pierre Le Gendre,&nbsp;Benoit Legras,&nbsp;Johann Kieffer","doi":"10.1002/aoc.70387","DOIUrl":"https://doi.org/10.1002/aoc.70387","url":null,"abstract":"<p>Heteroleptic and homoleptic complexes of zinc with phenoxyimine and phenoxyamidine ligands are used as alternatives to currently used tin catalysts in the transesterification reaction of methyl acrylate and <i>N,N-</i>dimethylethanolamine in the synthesis of <i>N,N-</i>dimethylaminoethyl acrylate. A large screening of phenoxyimine and three generations of phenoxyamidine ligands has been undertaken and used to determine the best catalysts in terms of conversion and selectivity. All of the catalysts tested show significant improvement in activity over catalysts currently well-established in industrial processes such as dibutyltin oxide or Ti(O^<i>i</i>Pr)₄. The catalytic charges can be decreased significantly (10–20×) still affording good conversions and selectivities. A series of heteroleptic and homoleptic zinc complexes with phenoxyimine and phenoxyamidine ligands have been tested for the transesterification of methyl acrylate with <i>N,N</i>-dimethylethanolamine. All the catalysts demonstrated a substantial increase in activity compared to dibutyltin oxide, a well-established catalyst that is currently used in industry for this reaction.</p>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/aoc.70387","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145223963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Study on the Adsorption Properties of Fe3O4@MnO2@β-Cyclodextrin Composite on Crystalline Violet and Mn (VII)","authors":"Yuhang Wang,&nbsp;Yong Ma","doi":"10.1002/aoc.70405","DOIUrl":"https://doi.org/10.1002/aoc.70405","url":null,"abstract":"<div>\u0000 \u0000 <p>Magnetic adsorption materials show great potential in wastewater treatment, but there are few relevant cases for the removal of crystalline violet (CV), while the removal of CV and heavy metal ions is even more of a challenge. In this experiment, Fe₃O₄ microspheres are used as the core and hydrothermally wrapped with stacked clusters of MnO₂ on the outside to increase the specific surface area of the composite. Finally, the Fe₃O₄@MnO₂ composite is wrapped with β-cyclodextrin (β-CD) by cross-linking grafting with the silane coupling agent KH-560, bringing a large number of O atoms and epoxy groups to the adsorbent. The prepared Fe₃O₄@MnO₂@β-CD composite has a large specific surface area of 209.897 m² g⁻¹ and has good removal of CV and Mn (VII). The effects of adsorbent type, initial concentration, temperature, and contact time on the adsorption performance were investigated. The results for the adsorption of CV and Mn (VII) show that the adsorption behavior follows a pseudo-second-order kinetic model and fits well with the Langmuir isotherm, indicating predominant monolayer adsorption, and the adsorption is governed by a combination of intraparticle and film diffusion mechanisms. Thermodynamic studies confirm its spontaneous and heat-absorbing nature. Remarkably, after five reuse cycles, there is minimal loss in removal rate. The prepared Fe₃O₄@MnO₂@β-CD composite is a green and renewable adsorbent, which has a wide application prospect in the adsorption field.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145223935","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}

{"title":"Synergistic Bifunctionality in Zn (II)-Porphyrin-Based Imidazolium Functionalized Porous Organic Polymers for Efficient Catalysis of CO2-Epoxide Cycloaddition","authors":"Peng Yan,&nbsp;Dongping Wang,&nbsp;Wenhua Xu,&nbsp;Ning Wang,&nbsp;Jun Li","doi":"10.1002/aoc.70404","DOIUrl":"https://doi.org/10.1002/aoc.70404","url":null,"abstract":"<div>\u0000 \u0000 <p>The development of bifunctional catalytic materials bearing Lewis acid and base activity sites toward the cycloaddition of CO₂ and epoxides to value-added cyclic carbonate under cocatalyst-free conditions is needed in particular. In this work, an imidazolium functionalized Zn (II)-porphyrin ZnTAEImP was first designed and synthesized. Subsequently, a series of porous organic polymers, named POP-ZnTAEImP/DVB(1:<i>m</i>) (<i>m</i> = 30, 50, 70), were prepared through the free-radical copolymerization of ZnTAEImP with divinylbenzene (DVB). The obtained POP-ZnTAEImP/DVB(1:<i>m</i>) exhibited a high specific surface area and good thermal stability. As bifunctional heterogeneous catalysts, POP-ZnTAEImP/DVB(1:<i>m</i>) showed excellent catalytic activities in CO₂ cycloaddition with epichlorohydrin under the condition of solvent-free. In particular, the POP-ZnTAEImP/DVB(1:50) demonstrated the highest catalytic activity (TON = 2880) and was applicable to a variety of epoxides. Furthermore, only a slight decrease in catalytic activity was observed after five cycles. Activation energy (<i>E</i>_<i>a</i>) for this reaction was determined to be 52.4 kJ/mol. This work provides a valuable strategy for designing efficient binary heterogeneous catalysts for the high-efficiency fixation of CO₂.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145223914","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}

{"title":"Heterobimetallic Pd-Ru Catalysts for the Synthesis of Functionalized Polynorbornenes via Reductive Heck/ROMP Reactions","authors":"Thais R. Cruz,&nbsp;Juliana I. P. Maia,&nbsp;Pedro I. S. Maia,&nbsp;Antonio E. H. Machado,&nbsp;Beatriz E. Goi,&nbsp;Lionel Delaude,&nbsp;Valdemiro P. Carvalho-Jr","doi":"10.1002/aoc.70401","DOIUrl":"https://doi.org/10.1002/aoc.70401","url":null,"abstract":"<p>Heterobimetallic complexes offer greater versatility for applications in homogeneous catalysis than their monometallic counterparts. To take advantage of this synergy, three [Pd(<i>N,N,S</i>-TSC)(4-NH₂Py)] complexes (<b>mono-Pd</b>^<b>Me</b>, <b>mono-Pd</b>^<b>Me,Me</b> and <b>mono-Pd</b>^<b>Ph</b>) were synthesized from [PdCl₂(MeCN)₂] and appropriate thiosemicarbazide (TSC) ligand precursors, followed by the addition of 4-aminopyridine (4-NH₂Py). The reaction of these mono-Pd^L complexes with [RuCl₂(η⁶-<i>p</i>-cymene)]₂ then afforded three heterobimetallic complexes with the generic formula [{RuCl₂(<i>p</i>-cymene)}-μ-{(4-NH₂Py)Pd (TSC)}] (<b>Ru-Pd</b>^<b>Me</b>, <b>Ru-Pd</b>^<b>Me,Me</b> and <b>Ru-Pd</b>^<b>Ph</b>). All these novel compounds were characterized by elemental analysis, spectroscopic techniques, cyclic voltammetry, and density functional theory (DFT) calculations. The molecular structure of <b>mono-Pd</b>^<b>Me</b> was determined by X-ray diffraction analysis. The Ru-Pd^L complexes were evaluated as bifunctional catalysts in the reductive Heck coupling of norbornadiene (NBD) with iodobenzene and the ring-opening metathesis polymerization (ROMP) of phenylnorbornene (Ph-NBE). They were very active for the reductive Heck reaction, reaching yields higher than 90% when a [Pd]/[NBD]/[PhI] ratio of 1/418/1344 was employed at 120°C. Upon activation with ethyl diazoacetate (EDA), they were also able to polymerize Ph-NBE with yields around 70% using a [Ph-NBE]/[Ru-Pd^L] ratio of 3000 at 50°C for 30 min. The <b>Ru-Pd</b>^<b>Me,Me</b> complex showed the highest activity in the ROMP of Ph-NBE and was successfully applied for mediating the synthesis of poly (Ph-NBE) from NBD via tandem catalysis.</p>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/aoc.70401","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197329","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"AIE Ligand-Based Luminescent Cd(II)-MOFs for Rapid and Selective Sensing of Pesticide DCN and Practical Application in Vegetable Samples","authors":"Qing-Yun Yang,&nbsp;Yi-Xuan Shi,&nbsp;Shu-Qing Yao,&nbsp;Yong Ju,&nbsp;Jing Ru","doi":"10.1002/aoc.70400","DOIUrl":"https://doi.org/10.1002/aoc.70400","url":null,"abstract":"<div>\u0000 \u0000 <p>Food safety issues have become society's focus and have been directly tied to consumer health. In order to guarantee food safety and public health, it was crucial to create innovative food testing methods that were effective, precise, and convenient. Herein, we successfully constructed two new luminescent metal–organic frameworks (MOFs) via solvothermal conditions, designated as [Cd₃(TFBA)₂(DMSO)₂(DIMB)]_n (<b>CdMOF-1</b>) and [Cd₃(TFBA)₂(DMSO)₂(DMIMB)]_n (<b>CdMOF-2</b>) (H₃TFBA = tris(3′-F-4′-carboxybiphenyl)amine, DIMB = 1,4-di(1H-imidazol-1-yl)butane), DMIMB = 1,4-di(1H-2-methylimidazol-1-yl) butane, DMSO = Dimethyl sulfoxide). <b>CdMOF-1</b> and <b>CdMOF-2</b> were investigated by single-crystal X-ray analysis and infrared spectroscopy (IR), X-ray powder diffraction (PXRD) and thermal gravimetric analysis (TGA). The fluorescence property studies demonstrated that <b>CdMOF-1</b> and <b>CdMOF-2</b> exhibited high selectivity, recyclability, and sensitivity in the detection of 2,6-dichloro-4-nitroaniline (DCN) in actual vegetable samples with low limited detection (LOD) of 0.499 μM, 0.480 μM for <b>CdMOF-1</b> and 0.308 μM, 0.380 μM for <b>CdMOF-2,</b> respectively. In situ imaging experiment results indicated that <b>CdMOF-1</b> and <b>CdMOF-2</b> have the potentiality to quickly and in situ identify pesticide residues on the surfaces of vegetable samples. Interestingly, mixed matrix membranes (MMMs) were also prepared for visual detection of DCN under 365 nm UV light. These findings exhibited that <b>CdMOF-1</b> and <b>CdMOF-2</b> could serve as portable luminescent sensors for the detection of DCN.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 11","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197178","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}

{"title":"Plant-Inspired Gold Nanoparticles (AuNPs)-Based Nanomedicine and Molecular Imaging for Breast Cancer Drug Delivery","authors":"Ravikant Shekhar,&nbsp;H. S. Prakash,&nbsp;Chandan Shivamallu,&nbsp;Shiva Prasad Panjala,&nbsp;Mostafa Abdelrahman,&nbsp;Sudisha Jogaiah,&nbsp;Nagaraj Geetha","doi":"10.1002/aoc.70409","DOIUrl":"https://doi.org/10.1002/aoc.70409","url":null,"abstract":"<div>\u0000 \u0000 <p>Breast cancer is the most commonly diagnosed malignancy among women worldwide, with treatment often challenged by genetic and non-genetic resistance mechanisms. This study presents a novel, eco-friendly approach for synthesizing gold nanoparticles (AuNPs) using the ethyl acetate extract of <i>Piper betle</i> var. Mysuru, an agriculturally significant plant known for its bioactive phytochemicals. This green synthesis method not only minimizes environmental impact but also enhances the therapeutic potential of the resulting nanoparticles. Characterization of the AuNPs revealed their spherical, nanocrystalline nature with a face-centered cubic lattice and diameters ranging from 14 to 34 nm (25 nm average). The AuNPs demonstrated remarkable cytotoxicity against MCF-7 breast cancer cell lines, achieving an IC₅₀ value of 9.06 ± 0.51 μg/mL, outperforming plant extracts and conventional therapies. Hemolytic assays further confirmed their safety, with minimal hemolysis (8.67%), supporting their potential for safe systemic circulation. The study's novelty is identifying decoside, a bioactive compound in <i>P. betle</i>, as a potent inhibitor of the EGFR signaling pathway. Molecular docking and dynamic simulations revealed strong binding interactions between decoside and target proteins, disrupting pathways critical to cancer cell proliferation. This work highlights the potential of <i>P. betle</i>-mediated AuNPs as a sustainable, scalable, and highly effective solution for breast cancer therapy. Their affordability, eco-friendliness, and enhanced therapeutic efficacy underscore their promise for clinical applications and large-scale production, paving the way for advanced cancer therapeutics with reduced side effects.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145146995","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}

{"title":"Formulation, Characterization, Antioxidant, Cytotoxicity, and Antiprostate Cancer Efficacies of Plant-Based Nanoparticles","authors":"Zehui Rao,&nbsp;Zhangjie Jiang,&nbsp;Chengyu Zou,&nbsp;Yida Zhang","doi":"10.1002/aoc.70353","DOIUrl":"https://doi.org/10.1002/aoc.70353","url":null,"abstract":"<div>\u0000 \u0000 <p>Here, we show how <i>Boswellia thurifera</i> extract may be used to bio-inspiredly synthesize zinc nanoparticles. <i>B. thurifera</i> was employed as an environmentally friendly medium that served as both an in situ stabilizer and a green reductant for the produced zinc nanoparticles. The intrinsic structural characteristics of the as-synthesized Zn NPs were studied by FE-SEM, EDX, XRD, and UV–Vis. Prostate cancer cell lines were used to evaluate the biogenic Zn NPs' antiprostate cancer capabilities. The MTT experiment showed that the Zn NPs could strongly inhibit the proliferation of LNCaP clone FGC-Luc2 cancer cells. In contrast to their corresponding control, Zn NPs prevent colony development. More importantly, the cells molecular pathway analysis treated with zinc nanoparticles showed that the extract increases the expression of p53 while suppressing the expression of STAT3 in cells. This suggests that STAT3 and p53 are the primary players responsible for the biological events that the extract triggers in human prostate cancer cells. Our data suggest that zinc nanoparticles might be a very promising anticancer drug against human prostate cancer cells.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145146570","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}

{"title":"A Zinc-Based Coordination Supramolecule Sensor for Sensitive Detection of Salbutamol Molecule","authors":"Ling Yue,&nbsp;Jingjing Qiao,&nbsp;Yefang Yang,&nbsp;Shaowen Qie,&nbsp;Zhilin Mu,&nbsp;Yongyang Chen,&nbsp;Yuejiao Jia,&nbsp;Ming Hu","doi":"10.1002/aoc.70406","DOIUrl":"https://doi.org/10.1002/aoc.70406","url":null,"abstract":"<div>\u0000 \u0000 <p>As a banned substance misused in doping drugs and lean meat powders, salbutamol (SAL) poses a potential threat to human health. Here, a luminescence zinc-based coordination supramolecule sensor was constructed from 2-(2′-pyridyl)benzimidazole-5-carboxylic acid (Hpbca) ligand and zinc sulfate in the self-assembly process under solvothermal conditions, namely, [Zn₂(pbca)₂(SO₄)(H₂O)₃] (<b>1</b>), which could function as an efficient fluorescence probe for the detection of SAL. The single-crystal X-ray diffraction analysis reveals that complex <b>1</b> possesses distinctive binuclear building units, which are interlinked to form a three-dimensional supramolecule framework through the interactions of π···π stacking and hydrogen bonding. Complex <b>1</b> demonstrated exceptional performances with a high sensitivity (the limit of detection: 0.357 ppm), excellent anti-interference, and rapid response time. The fluorescence sensing mechanism of complex <b>1</b> toward SAL was systematically investigated through comprehensive experiments and DFT calculations. For practical implementations, we developed portable low-cost test strips by incorporating complex <b>1</b> into polymer materials, which enabled visual SAL detection through distinct color changes under the UV irradiation of 365 nm. These composite films exhibited reliable performance in recognizing SAL with the naked eye, offering promising feasibility for on-site monitoring in the fields of anti-doping and food safety.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145146472","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}

{"title":"Adroit Green Synthesis of Silver Nanoparticles: Multivariate Photocatalytic Degradation of Alizarin Yellow R Dye and Biomedical Applications","authors":"Manojna R. Nayak,&nbsp;Ravindra R. Kamble,&nbsp;Vishwa B. Nadoni,&nbsp;Arun K. Shettar,&nbsp;Joy H. Hoskeri,&nbsp;Rangappa S. Keri","doi":"10.1002/aoc.70397","DOIUrl":"https://doi.org/10.1002/aoc.70397","url":null,"abstract":"<div>\u0000 \u0000 <p>In an effort to address the issues of water pollution, it is crucial to foster extremely durable and solar light-sensitive photocatalysts for accelerating the elimination of organic dyes from wastewater. Solar-driven photocatalytic dye degradation has been touted as a novel, feasible, and economical method as it leverages an interminable and renewable energy source. In this study, liquid jaggery, a natural and renewable reducing agent, was employed for the synthesis of silver nanoparticles (Ag NPs) under ambient conditions. Various analytical techniques are used to ascertain morphological, structural, and compositional characteristics. The catalytic activity of prepared Ag NPs was assessed on alizarin yellow R (AYR) as a pollutant organic dye. The produced silver nanoparticles (Ag NPs) displayed efficacious photocatalytic activity when tested against the AYR dye. A systematic investigation was undertaken to elucidate the effects of critical reaction parameters, including temperature, pH, exposure duration, and catalyst dosage, on the solar-driven photocatalytic decomposition of AYR dye. Remarkably, the Ag NPs exhibited outstanding catalytic efficacy, achieving an impressive 95.87% degradation within 30 h, underscoring their substantial potential for advanced wastewater treatment and environmental remediation. Furthermore, the study underscores the versatile nature of Ag NPs, extending their applicability beyond environmental remediation to advanced biomedical domains. These applications include their utilization as antimicrobial agents in dentistry and dental implants, antitumor agents, antidiabetic, and facilitators of wound healing. The dual functionality of Ag NPs, bridging sustainable environmental technologies and innovative biomedical solutions, highlights their transformative potential in addressing contemporary scientific and technological challenges.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145110932","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}

{"title":"Enhanced Photocatalytic, Mechanical, and Optical Performance of Rare-Earth–Doped Mg₂Si: First-Principles Calculations and Machine Learning","authors":"Jianfeng Ye,&nbsp;Xinhai Wang,&nbsp;Dahai Yu,&nbsp;Fuqiang Ai,&nbsp;Songguo Yu,&nbsp;Jiayi Shen,&nbsp;Shenshang Lu,&nbsp;Qingquan Xiao,&nbsp;Shen Li,&nbsp;Quan Xie","doi":"10.1002/aoc.70396","DOIUrl":"https://doi.org/10.1002/aoc.70396","url":null,"abstract":"<div>\u0000 \u0000 <p>Broadband light absorption, mechanical resilience, and efficient surface catalysis are all crucial for photocatalytic semiconductors, yet they are rarely improved together in one material. We combine first-principles calculations with machine-learning interpretability and Pearson correlation analyses to reveal that rare-earth (La, Er) doping of Mg₂Si can synergistically enhance its optoelectronic, mechanical, and hydrogen-evolution performance. La doping introduces conduction-band impurity states via La-5d/Si-3p orbital hybridization, boosting sub-bandgap (infrared) absorption by 60-fold (~0.6 × 10⁵ cm⁻¹) and extending the absorption edge into the near-infrared—translating to a solar-to-hydrogen conversion efficiency of up to 39.86%. It also percolates a metallic bond network that doubles the Poisson's ratio (0.23 → 0.46), transforming Mg₂Si from brittle to ductile. Er doping, in contrast, localizes 4f orbitals, yielding exciton-like absorption peaks (~10⁵ cm⁻¹) in the ultraviolet and inducing a distinct electronic and mechanical response. Both dopants push the Fermi level into the conduction band (degenerate n-type doping), fundamentally altering carrier characteristics. Catalytically, La doping generates delocalized sp³d² orbitals that give near-thermoneutral hydrogen adsorption (Δ<i>G</i>_<i>H*</i> ≈ −0.04 eV), outperforming noble-metal catalysts, whereas Er's extended electron density enhances H binding at the cost of slower H₂ desorption. SHAP (SHapley Additive exPlanations) analysis further identifies the key orbital and elastic descriptors governing these trends, providing a mechanistic blueprint.</p>\u0000 </div>","PeriodicalId":8344,"journal":{"name":"Applied Organometallic Chemistry","volume":"39 10","pages":""},"PeriodicalIF":3.7,"publicationDate":"2025-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145102028","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}