Inorganic Chemistry最新文献_第4页

Unlocking Improved Formic Acid Dehydrogenation of Pd Nanoparticles Immobilized on Amine-Functionalized Yolk–Shell Silica

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.4c05024

Chunhui Zhou, Hao Chai, Rongmei Zhang, Youcheng Feng, Jinsong Hu, Haidong Li, Xiu Chen, Zhentao Liu, Chunming Xu, Xilong Wang

{"title":"Unlocking Improved Formic Acid Dehydrogenation of Pd Nanoparticles Immobilized on Amine-Functionalized Yolk–Shell Silica","authors":"Chunhui Zhou, Hao Chai, Rongmei Zhang, Youcheng Feng, Jinsong Hu, Haidong Li, Xiu Chen, Zhentao Liu, Chunming Xu, Xilong Wang","doi":"10.1021/acs.inorgchem.4c05024","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05024","url":null,"abstract":"In this work, a series of mesoporous yolk–shell silica spheres (YS-x) with tunable yolk size and shell thickness were synthesized via the incubation method in water. Following amination and Pd loading treatment on YS-x, a series of catalysts Pd-YS-x-NH2 were obtained successfully and applied to formic acid (FA) dehydrogenation for hydrogen (H2) generation. The optimal catalyst Pd-YS-6-NH2, which has an appropriate yolk size and shell thickness, the largest specific surface area, and pore volume, as well as the smallest Pd nanoparticles (NPs), exhibits dehydrogenation performance far superior to that of other reference catalysts. It shows an extraordinary turnover frequency (TOF, 4508 h–1) and excellent stability at 60 °C with sodium formate (SF). After five testing cycles, it still maintained 100% FA conversion, and the decline in catalytic performance is almost negligible. The excellent catalytic performance of Pd-YS-6-NH2 is attributed to the optimal yolk–shell structure, the introduction of amine groups, and highly dispersed and ultrasmall Pd NPs (1.5 nm). This study provides methods for yolk–shell catalyst design and development for FA dehydrogenation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435744","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

A High-Stability Co-MOF with Open Metal Sites for C2H2/CO2/CH4 Separation

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.5c00327

Tianyi Hou, He Wang, Yuan-Yuan Zhang, Zhengyi Di, Cheng-Peng Li

引用次数: 0

Dual Activation of N₂ and CO₂ toward N-O Coupling by Single Copper Ions.

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.4c05483

Qiuhao Yi, Chaonan Cui, Demiao Ma, Zhixun Luo

引用次数: 0

Sn(II)-Pyrophosphate Complex with Low Plating/Stripping Potential for Sn-I Flow Battery Applications.

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.5c00248

Shengwen Tan, Dunyong He, Tian Xu, Rui Fang, Yanrong Wang, Guowang Diao, Caixing Wang

引用次数: 0

Unmasking the UV Photobleaching of β-Diketonate [Eu(BTFA)4]− Complexes as an Energy-Driven Photoreduction Process

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.4c05014

Lizandra L. L. S. Melo, Gerson P. Castro, Jr., Marcelo Navarro, Simone M. C. Gonçalves, Alfredo M. Simas

{"title":"Unmasking the UV Photobleaching of β-Diketonate [Eu(BTFA)4]− Complexes as an Energy-Driven Photoreduction Process","authors":"Lizandra L. L. S. Melo, Gerson P. Castro, Jr., Marcelo Navarro, Simone M. C. Gonçalves, Alfredo M. Simas","doi":"10.1021/acs.inorgchem.4c05014","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05014","url":null,"abstract":"We elucidate the nature of the gradual attenuation of luminescence under sustained ultraviolet (UV) radiation exposure in europium [Eu(BTFA)4]− complexes, revealing that it originates from a nonlinear energy-driven process, wherein Eu(III) is irreversibly reduced to Eu(II). This photoreduction was confirmed via the electrochemical techniques cyclic voltammetry and chronoamperometry, which, coupled with luminescence experiments, provided direct evidence of the Eu3+/Eu2+ reduction and the disappearance of Eu(III) after UV exposure. Indeed, extended UV exposure induces a gradual decrease in Eu(III) luminescence, paired with an increased intensity of Eu(II) luminescence, upon direct excitation of the metal ion. To provide an adequate description of this process, we advanced a photochemical law in the energy domain (rather than the time domain) and introduced the concept of photobleaching energy to facilitate comparisons of photostability among various complexes in different solvents. The nonlinearities detected in the energy domain suggest an underlying multiphoton process. As a consequence, we uncovered a trade-off between photostability and luminescence: enhancing one implies diminishing the other. Specifically, the proximity between the complex and cation in nonpolar solvents induces asymmetry in the complex, enhancing luminescence but reducing photostability. Conversely, distancing the cation leaves the complex within a more symmetrical solvent enclosure, decreasing luminescence and increasing photostability. Our findings also indicate that exposing Eu(III) complexes to UV light can function as a method for the photochemical synthesis of Eu(II) complexes, a process further substantiated by our electrochemical experiments.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435722","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

Two Plus Four Equals Three-Iron(II)/Iron(IV) Comproportionation as an Additional Pathway for Iron(IV)-Oxido Reactions.

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.4c04518

Niko S W Lindlar Né Jonasson, Annika Menke, Laura Senft, Andrea Squarcina, David Schmidl, Katherine Fisher, Serhiy Demeshko, Jan C Kruse, Thomas Josephy, Peter Mayer, Jonathan Gutenthaler-Tietze, Peter Comba, Franc Meyer, Ivana Ivanović-Burmazović, Lena J Daumann

{"title":"Two Plus Four Equals Three-Iron(II)/Iron(IV) Comproportionation as an Additional Pathway for Iron(IV)-Oxido Reactions.","authors":"Niko S W Lindlar Né Jonasson, Annika Menke, Laura Senft, Andrea Squarcina, David Schmidl, Katherine Fisher, Serhiy Demeshko, Jan C Kruse, Thomas Josephy, Peter Mayer, Jonathan Gutenthaler-Tietze, Peter Comba, Franc Meyer, Ivana Ivanović-Burmazović, Lena J Daumann","doi":"10.1021/acs.inorgchem.4c04518","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04518","url":null,"abstract":"Iron enzymes are ubiquitous in nature. In particular, enzymes with iron-oxygen cofactors as active sites perform a vast variety of reactions. Both iron(III)-hydroxido and iron(IV)-oxido species have been observed to play a catalytically active role. In order to complement biochemical investigations, a large variety of synthetic compounds using these motifs were synthesized in past decades to study and understand their inherent reactivity. One such synthetic model complex is [FeIV(O)(Py5Me2)]2+, (Py5Me2 = 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine, henceforth labeled L1), which was used as a model complex for epigenetically relevant iron(II)/α-ketoglutarate-dependent ten-eleven translocation 5-methylcytosine dioxygenases (TET). Additionally, [FeIII(OH)(Py5(OH)2)]2+ (Py5(OH)2 = pyridine-2,6-diylbis [di(pyridin-2-yl)methanol, henceforth labeled L2) was tested as a lipoxygenase model. We have complemented the available complexes of these related pentapyridyl complexes to include all oxidation states II-IV and performed detailed spectroscopic and spectrometric investigations. We found that iron(II) and iron(IV)-oxido compounds (cross-)comproportionate readily to form iron(III)-hydroxido species, which represents a major side reaction for model complex investigations. We also investigated the oxidative reactivity of a new iron(IV)-oxido complex.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447287","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

In Situ Synthesis of Highly Emissive Manganese Halides with Modified Bisphosphonium Cations toward Information Encryption.

IF 4.3 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.4c05594

Xuan Zou, Xiangyu Han, Gangji Yi, Zhizhuan Zhang, Xize Zhan, Hongmei Zeng, Zhien Lin, Guohong Zou

{"title":"In Situ Synthesis of Highly Emissive Manganese Halides with Modified Bisphosphonium Cations toward Information Encryption.","authors":"Xuan Zou, Xiangyu Han, Gangji Yi, Zhizhuan Zhang, Xize Zhan, Hongmei Zeng, Zhien Lin, Guohong Zou","doi":"10.1021/acs.inorgchem.4c05594","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05594","url":null,"abstract":"Multisite modulation for organic-inorganic hybrid metal halides (OIMHs) plays an important role in the optimization of their photophysical performance. Herein, we proposed an organic cation modification strategy on the phosphorus sites based on 1,2-Bis(diphenylphosphino)ethane (DPPE) by a simple one-pot solvothermal method. Three zero-dimensional (0D) manganese-based OIMHs, two novel MdppeMnCl4·H2O and EdppeMnCl4, as well as the byproduct [Mn(dppeO2)3][MnCl4] were obtained (Mdppe = methyl-coordinated with DPPE; Edppe = ethyl-coordinated with DPPE; and dppeO2 is obtained by oxidation of DPPE). All the samples possess the four-coordinated [MnCl4]2- polyhedron, while [Mn(dppeO2)3][MnCl4] contains another six-coordinated cation [Mn(dppeO2)3]2+ complex. According to the relevant optical measurements, MdppeMnCl4·H2O and EdppeMnCl4 both show bright green emissions with photoluminescence quantum yields of 55.66% and 80.42%, respectively. By contrast, [Mn(dppeO2)3][MnCl4] shows an orange emission that is confirmed to be associated with six-coordinated Mn2+ ions by temperature-dependent PL spectra. Based on the good stability and solution processability of EdppeMnCl4, a luminescent ink was developed and shows potential application in display and information encryption fields. The unique cation modification strategy in this work opens up the ways for designing and developing novel OIMHs and extends the application prospects of manganese-based halides.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143447279","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

Lanthanide Oxalates: From Single Crystals to 2D Functional Honeycomb Nanosheets

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.4c04293

Daniela Veronika Uríková, Giannis Kampitakis, Ivana Císařová, Adam Alemayehu, Matouš Kloda, Dominika Zákutná, Kamil Lang, Jan Demel, Václav Tyrpekl

{"title":"Lanthanide Oxalates: From Single Crystals to 2D Functional Honeycomb Nanosheets","authors":"Daniela Veronika Uríková, Giannis Kampitakis, Ivana Císařová, Adam Alemayehu, Matouš Kloda, Dominika Zákutná, Kamil Lang, Jan Demel, Václav Tyrpekl","doi":"10.1021/acs.inorgchem.4c04293","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04293","url":null,"abstract":"Oxalates are simple, low-cost but crucial compounds in the technology of lanthanides, actinides, and transition metals. Apart from using oxalate as a versatile ligand in coordination chemistry, simple oxalate salts are still under a scientific focus, linked with ion batteries, optical and magnetic materials, and, most importantly, industrial-technological mining and separation loops. The typically low solubility of oxalate salts is advantageous from the viewpoint of a convenient and affordable synthesis requiring only green solvents. Even though basic lanthanide oxalates have been known for decades, their structural descriptions have remained fuzzy, especially concerning water content and heavy lanthanide analogues. Herein, we present a newly developed preparation technique for large oxalate monocrystals applied to the whole lanthanide series. All of the structures were reviewed, and some new structures were determined. All of these oxalates exhibit a honeycomb structure with closed cavities containing water molecules. These honeycomb coordination polymers form a layered structure bonded by hydrogen bonds. Surprisingly, most oxalates can be easily exfoliated/delaminated in EtOH, forming colloids of up to single-layered nanosheets. Such a feature has never been described for 2D lanthanide oxalates and demonstrates a new form of applicability for them, e.g., for the construction of thin films or inkjet-printed layers using an extremely facile and economical preparation route.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"51 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435720","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

Ru(II)-Fenamic-Based Complexes as Promising Human Ovarian Antitumor Agents: DNA Interaction, Cellular Uptake, and Three-Dimensional Spheroid Models

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.4c04344

Tamara Teixeira, Marcos V. Palmeira-Mello, Pedro Henrique Machado, Carlos A. F. Moraes, Camila Pinto, Rayane C. Costa, Wladimir Badaró, José A. Gomes Neto, Javier Ellena, Fillipe Vieira Rocha, Alzir A. Batista, Rodrigo S. Correa

{"title":"Ru(II)-Fenamic-Based Complexes as Promising Human Ovarian Antitumor Agents: DNA Interaction, Cellular Uptake, and Three-Dimensional Spheroid Models","authors":"Tamara Teixeira, Marcos V. Palmeira-Mello, Pedro Henrique Machado, Carlos A. F. Moraes, Camila Pinto, Rayane C. Costa, Wladimir Badaró, José A. Gomes Neto, Javier Ellena, Fillipe Vieira Rocha, Alzir A. Batista, Rodrigo S. Correa","doi":"10.1021/acs.inorgchem.4c04344","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04344","url":null,"abstract":"Cancer resistance to chemotherapeutic agents such as cisplatin presents a significant challenge, leading to treatment failure and poor outcomes. Novel metal-based compounds offer a promising strategy to overcome drug resistance and to enhance efficacy. Four Ru(II) complexes with fenamic acid derivatives were synthesized and characterized: [Ru(L)(bipy)(dppp)]PF6, where L represents fenamic acid (HFen, complex 1), mefenamic acid (HMFen, complex 2), tolfenamic acid (HTFen, complex 3), and flufenamic acid (HFFen, complex 4). Their composition was supported by molar conductivity, elemental analysis, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, mass spectrometry, and 31P{1H}, 1H, and 13C nuclear magnetic resonance, with the crystal structure of complex 1 confirmed via X-ray diffraction. Complexes 1–4 exhibited notable cytotoxicity against tested cell lines, particularly A2780 and A2780cisR (cisplatin-resistant ovarian tumors), compared to MDA-MB-231 (breast) and A549 (lung) lines. Mechanistic studies revealed weak DNA interactions through minor grooves or electrostatic binding. Cellular uptake assays showed effective internalization of complexes 1 (3.6%) and 2 (4.5%), correlating with potent IC50 values. These complexes also altered cell morphology, reduced cell density, and inhibited colony formation in the A2780 cells. Staining assays indicated induced cell death and organelle damage, highlighting their potential as promising antitumor agents.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435721","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

Structural Regularities, Thermal Stability, and Nature of Chemical Bonding in the Series of Actinide Double Sulfates Cs[An(SO4)2(H2O)3]·H2O (An = U, Np, Pu, or Am)

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-02-18 DOI: 10.1021/acs.inorgchem.4c04102

Tatiana Poliakova, Iurii Nevolin, Andrey Shiryaev, Alexander Fedoseev, Mikhail Grigoriev, Alexey Averin, Vladislava Zubkova, Daniil Novichkov, Alexander Trigub, Anna Krot, Mikhail Volgin, Petr Matveev

{"title":"Structural Regularities, Thermal Stability, and Nature of Chemical Bonding in the Series of Actinide Double Sulfates Cs[An(SO4)2(H2O)3]·H2O (An = U, Np, Pu, or Am)","authors":"Tatiana Poliakova, Iurii Nevolin, Andrey Shiryaev, Alexander Fedoseev, Mikhail Grigoriev, Alexey Averin, Vladislava Zubkova, Daniil Novichkov, Alexander Trigub, Anna Krot, Mikhail Volgin, Petr Matveev","doi":"10.1021/acs.inorgchem.4c04102","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04102","url":null,"abstract":"Investigation of the properties of the trivalent light actinide compounds is hindered by their low stability under normal conditions. In this study, the An3+ double sulfates Cs[An(SO4)2(H2O)3]·H2O (An = U, Np, Pu, or Am) were synthesized and characterized by complementary methods. Their structure was solved using single-crystal X-ray diffraction (XRD), and peculiarities of the sulfate anion environment were addressed with vibrational spectroscopy. The oxidation states of the actinides were confirmed by using X-ray absorption near edge spectroscopy (XANES) and solid-state absorption spectroscopy. Changes in the local environment of Am ions caused by self-irradiation are observed after several months of storage. Decomposition of the compounds in air and in the inert atmosphere at temperatures up to 1000 °C and the final products were studied using thermal analysis and powder diffraction. Computational investigation employing approaches such as QTAIM, Löwdin bond order analysis, and atomic charge calculations was used to investigate trends in the nature of chemical bonds in these compounds. It is shown that the covalent interaction decreases from U to Am with a corresponding increase in ion charge.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"55 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435719","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