Inorganic Chemistry最新文献_第5页

Supramolecular Eu(III)4L4 Tetrahedra-Based Films for Luminescence Sensing of Volatile Amines with Sub-ppt-Level Detection Limit

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.4c05480

Yang Zhou, Fan Yin, Shao-Jun Hu, Li-Peng Zhou, Jian Yang, Qing-Fu Sun

引用次数: 0

In Situ Assembly Engineering-Induced 3D MOF-Driven MXene Framework for Highly Stable Na Metal Anodes

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.4c04230

Yiming Zhang, Zhipeng Li, Baihua Qu, Xing Shen, Le Tong, Jin Wang, Jingqin Cui, Xin Li, Qingshui Xie, Jingfeng Wang

{"title":"In Situ Assembly Engineering-Induced 3D MOF-Driven MXene Framework for Highly Stable Na Metal Anodes","authors":"Yiming Zhang, Zhipeng Li, Baihua Qu, Xing Shen, Le Tong, Jin Wang, Jingqin Cui, Xin Li, Qingshui Xie, Jingfeng Wang","doi":"10.1021/acs.inorgchem.4c04230","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04230","url":null,"abstract":"Sodium metal, with its high theoretical capacity, low redox potential, and cost-effectiveness, presents a promising anode candidate for next-generation high-energy-density batteries. However, the development of Na metal anodes is significantly challenged by issues such as uncontrolled dendrite growth, uncontrolled volume expansion, and associated safety concerns. Designing and developing advanced materials to enhance the conductivity of sodium metal anodes and promote uniform sodium ion deposition are of urgent importance. Herein, a MXene-based hybrid material was developed by integrating MOF-derived Zn, Co, N, and C dopants with Ti3C2Tx MXene to serve as a hosting substrate for the Na metal anode. The MXene provided a conductive framework, while the MOF-derived dopants introduced sodiophilic sites, promoting uniform Na deposition and mitigating volume expansion. The optimized material demonstrated an average Coulombic efficiency of 99.99% over 3000 cycles and stable cycling for over 5000 h in symmetrical cells and maintained over 80% capacity retention at 3 C after 500 cycles in full-cell tests, highlighting its potential as a robust Na metal anode material.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"63 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723800","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

Role of Solvent Decomposition in the Synthesis and Composition of Porous Zirconium-Based Coordination Cages

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.4c04982

Rebecca X. Skalla, Christine M. Montone, Maren Pink, Olivia K. Walters, Eric D. Bloch

{"title":"Role of Solvent Decomposition in the Synthesis and Composition of Porous Zirconium-Based Coordination Cages","authors":"Rebecca X. Skalla, Christine M. Montone, Maren Pink, Olivia K. Walters, Eric D. Bloch","doi":"10.1021/acs.inorgchem.4c04982","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c04982","url":null,"abstract":"Porous zirconium-based coordination cages are promising materials for applications in gas adsorption, catalysis, and molecular separation due to their tunability and stability. However, their synthesis is often complicated by the formation of competing phases, including insoluble or poorly soluble byproducts that impact purity and composition. Moreover, product composition and solubility can vary widely due to factors such as humidity, seasonal fluctuations, and lab-to-lab variations, highlighting the inherent lack of robustness in these syntheses. In this work, we investigate how solvothermal synthesis conditions, particularly temperature and solvent decomposition, influence the formation and composition of these cages. We show that elevated temperatures accelerate solvent breakdown, leading to the incorporation of formate and acetate byproducts that alter the final cage structures and contribute to the formation of insoluble zirconium-based, amorphous solids. By systematically varying the reaction conditions, we optimized the composition of the isolated cage products, achieving improved phase purity. By optimizing synthetic parameters, we achieve control over cage formation and particle morphology while mitigating the effects of solvent decomposition. Our findings provide insights into the balance between ligand coordination and solvent effects, enabling the development of strategies to enhance the purity, porosity, and functionality of these molecular cages.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"29 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713617","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

SUF4: A Terminal Monosulfido Complex of Uranium(VI) with a Linear SUF Moiety

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.4c05157

Qingxiu He, Xiuting Chen, Yu Gong

{"title":"SUF4: A Terminal Monosulfido Complex of Uranium(VI) with a Linear SUF Moiety","authors":"Qingxiu He, Xiuting Chen, Yu Gong","doi":"10.1021/acs.inorgchem.4c05157","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05157","url":null,"abstract":"Although there have been a few terminal sulfido complexes of uranium(VI) with either SUO or SUN moiety, it remains a question whether the terminal sulfido ligand can be stabilized in the absence of such multiply bound oxo or nitrido ligands. Herein, we report a terminal monosulfide complex of uranium(VI) in the form of SUF4 bearing a linear SUF moiety that was prepared via the reaction of laser-ablated uranium atoms with SF4 in cryogenic matrixes. On the basis of the results from infrared spectroscopy combined with density functional theory calculations at the B3LYP level, the SUF4 complex possesses a trigonal bipyramid structure with singlet ground state and nonplanar C3v symmetry where the terminal sulfido ligand is stabilized by the monovalent fluoro ligand trans to sulfur. A triple U–S bond with a positively charged sulfur atom was identified according to the natural bond orbital analysis. Inverse trans influence is present in SUF4 as revealed by the difference in bond length between U–Faxial from the linear SUF moiety and U–Fequatorial from the UF3 equatorial plane, which is further supported by bonding analysis.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"72 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713618","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

Luminescent Iridium-Peptide Nucleic Acid Bioconjugate as Photosensitizer for Singlet Oxygen Production toward a Potential Dual Therapeutic Agent

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.4c05359

Rosa Maria Dell’Acqua, Veronica Schifano, Maria Vittoria Dozzi, Laura D’Alfonso, Monica Panigati, Paola Rusmini, Margherita Piccolella, Angelo Poletti, Silvia Cauteruccio, Daniela Maggioni

{"title":"Luminescent Iridium-Peptide Nucleic Acid Bioconjugate as Photosensitizer for Singlet Oxygen Production toward a Potential Dual Therapeutic Agent","authors":"Rosa Maria Dell’Acqua, Veronica Schifano, Maria Vittoria Dozzi, Laura D’Alfonso, Monica Panigati, Paola Rusmini, Margherita Piccolella, Angelo Poletti, Silvia Cauteruccio, Daniela Maggioni","doi":"10.1021/acs.inorgchem.4c05359","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05359","url":null,"abstract":"A novel bioorganometallic PNA conjugate (Ir-PNA) was synthesized by covalently bonding a model PNA tetramer to a luminescent bis-cyclometalated Ir(III) complex that acted as a photosensitizer under light irradiation to generate singlet oxygen (1O2). The conjugate was prepared using an Ir complex bearing the 1,10-phenanthroline ligand functionalized with either a free primary amine (Ir-NH2) or a carboxyl group (Ir-COOH) for the conjugation to PNA. The photophysical studies on the Ir-COOH and the Ir-PNA demonstrated that the luminescent properties were maintained after the conjugation of the Ir fragment to PNA. Furthermore, the abilities to produce 1O2 of Ir-COOH and Ir-PNA were confirmed in a cuvette under visible light irradiation employing 1,5-dihydroxynaphthalene as a reporter, and the measured singlet oxygen quantum yield (ΦΔ) supported the Ir-PNA conjugate efficacy as a photosensitizer (ΦΔ = 0.54). Two-photon absorption microscopy on HeLa cells revealed that Ir-PNA localized in both the cytosol and nucleus, suggesting its potential as an intracellular carrier for PNA. Cytotoxicity assays by MTT tests showed that Ir-PNA was nontoxic in the absence of light, but induced cell death (EC50 = 18 μM) after UV irradiation. Overall, the Ir-PNA conjugate represents a promising system for the intracellular delivery of the PNA and its application in PDT.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723801","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

Enhanced Oxidative Coupling of Thiols to Disulfides Using the Visible-Light-Responsive POM@MOF Constructed with Ru Metalloligands

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.5c00125

Luoning Li, Yanan Liu, Jing Wang, Minzhen Cai, Pengtao Ma, Jingping Wang, Jingyang Niu

{"title":"Enhanced Oxidative Coupling of Thiols to Disulfides Using the Visible-Light-Responsive POM@MOF Constructed with Ru Metalloligands","authors":"Luoning Li, Yanan Liu, Jing Wang, Minzhen Cai, Pengtao Ma, Jingping Wang, Jingyang Niu","doi":"10.1021/acs.inorgchem.5c00125","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00125","url":null,"abstract":"The photocatalytic oxidative coupling of thiols to disulfides by using visible light represents an economically viable and environmentally sustainable strategy. A novel POM@MOF photocatalyst (Ru–CdS–SiW) was synthesized through the encapsulation of Keggin-type [SiW12O40]4– within a MOF composed of Ru metalloligands and {Cd4S2O16} clusters. In this structure, the incorporation of POMs to the MOFs reduced the charge transport distance, facilitated the separation and transfer of photogenerated charges and holes, and prevented the recombination of electron–hole pairs. The Ru–CdS–SiW catalyst demonstrated exceptional catalytic performance, achieving a 98.1% yield in the S–S bond formation from 4-methylthiophenol coupling with an apparent quantum yield of 4.8% at 440 nm. Through comprehensive exploratory experiments and electron paramagnetic resonance (EPR) measurements, we elucidated the mechanism underlying the photoinduced oxidative coupling of thiols. Notably, this catalytic reaction operates under mild visible-light conditions and exhibits remarkable recyclability, presenting significant potential for applications in sensitive systems, such as protein disulfide bond formation.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"81 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713582","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

Synthesis and Photophysics of the Doubly Cyclometalated Pd(II) Complexes [Pd(C∧N∧C)(L)], L = PPh3, AsPh3, and SbPh3

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.4c05436

Rose Jordan, Sam Kler, Iván Maisuls, Niklas Klosterhalfen, Benjamin Dietzek-Ivanšić, Cristian A. Strassert, Axel Klein

{"title":"Synthesis and Photophysics of the Doubly Cyclometalated Pd(II) Complexes [Pd(C∧N∧C)(L)], L = PPh3, AsPh3, and SbPh3","authors":"Rose Jordan, Sam Kler, Iván Maisuls, Niklas Klosterhalfen, Benjamin Dietzek-Ivanšić, Cristian A. Strassert, Axel Klein","doi":"10.1021/acs.inorgchem.4c05436","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05436","url":null,"abstract":"While Pt(II) complexes containing doubly cyclometalated ligands as tridentate luminophores are well studied, the synthetic accessibility of their Pd(II) counterparts was lacking for a long time. Inspired by a recent report on the synthesis of [Pd(dpp)(PPh3)] involving the C∧N∧C coordination mode (with dpp2– = 2,6-di(phenid-2-yl)pyridine) and following our own work on closely related Pt(II)-based compounds, we produced the series of complexes [Pd(dpp)(PnPh3)] (Pn = P, As, Sb) by optimizing the synthetic procedure and exploring their reactivity in the process. Our study of the electrochemical (cyclic voltammetry) and photophysical (UV–vis absorption and emission, transient absorption (TA) spectroscopy) properties of the Pd(C∧N∧C) complexes represents the first report on their characterization. We observed UV–vis absorption bands down to 450 nm and electrochemical HOMO–LUMO gaps around 3.2 V, which show minimal variation with different PnPh3 coligands. A more pronounced influence of the coligand was observed in time-resolved emission and TA spectroscopy. The highest photoluminescence quantum yield (ΦL) in the series was found for [Pd(dpp)(AsPh3)], reaching 0.06. The interpretation of the spectroscopic data is supported by (TD-)DFT calculations. Additionally, we report structural and spectroscopic data for several dinuclear Pd(II) complexes, including the precursor {[Pd(dppH)(μ-Cl)]}2 and multiple decomposition products of the sensitive compounds [Pd(dpp)(PnPh3)].","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"125 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713619","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

SCSC Transformation of Heterobimetallic 2D MOF to Homometallic 2D MOF via Solvent-Assisted Removal of Second Metal Component: An Add-and-Remove Strategy

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-26 DOI: 10.1021/acs.inorgchem.4c05422

Seulgi Kim, Taehun Kim, Kyunghye Ju, Je Hyun Bae, In-Hyeok Park

{"title":"SCSC Transformation of Heterobimetallic 2D MOF to Homometallic 2D MOF via Solvent-Assisted Removal of Second Metal Component: An Add-and-Remove Strategy","authors":"Seulgi Kim, Taehun Kim, Kyunghye Ju, Je Hyun Bae, In-Hyeok Park","doi":"10.1021/acs.inorgchem.4c05422","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05422","url":null,"abstract":"Constructing high-dimensional metal–organic framework (MOF) materials that cannot be reached by direct methods is demanding. We herein report the construction of a two-dimensional (2D) copper(I) iodide MOF via an add-and-remove strategy of a second metal component (HgI2). The networking reaction of an O2S2-macrocycle (L) with CuI via a bridging exocyclic coordination under the direct condition was unsatisfactory because of its one-dimensional (1D) product {[(μ4-Cu3I3)(L)2]·2CH3CN·CH2Cl2}n (1) with low yield. Alternatively, the self-assembly of L with a mixture of CuI and HgI2 allows the generation of a 2D heterobimetallic Cu(I)/Hg(II)-MOF {[Cu2(μ-Hg2I4)(L)2(CH3CN)2I2]·toluene}n (2, brick wall) cross-linked by μ-Hg2I4 square dimers via the bridging exocoordination mode. When the crystals of 2 were immersed in methanol, the crystals were converted to a desired 2D Cu(I)-MOF [(μ4-Cu2I2)(L)2]n (3, square grid) by the replacement of the cross-linker μ-Hg2I4 with μ4-Cu2I2 via the solvent-assisted etching. Interestingly, this 2D–[1D]*–2D conversion process that proceeds in an SCSC mode is completed by the dimerization of open coordinating site CuI* to form a μ4-Cu2I2 node (2CuI* → Cu2I2), preserving the 2D dimensionality. The conversion process is discussed based on PXRD, EDX, AFM, TGA, and NMR data.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713654","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

Metal-Induced Amide Deprotonation and Binding Typical for Cu(II), Not Possible for Zn(II) and Fe(II) 金属诱导的酰胺去质子化和结合对 Cu(II) 典型，对 Zn(II) 和 Fe(II) 不可能

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-26 DOI: 10.1021/acs.inorgchem.5c00672

Silvia Leveraro, Valentyn Dzyhovskyi, Kinga Garstka, Agnieszka Szebesczyk, Fabio Zobi, Denise Bellotti, Kamila Stokowa-Sołtys, Maurizio Remelli, Magdalena Rowińska-Żyrek

引用次数: 0

Design of Core@Shell Nanoparticles Based on Gold and Magnetic NiFe Prussian-Blue Analogues Featuring Shape-Dependent Magnetic and Electrochemical Activity

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-26 DOI: 10.1021/acs.inorgchem.4c05320

Shoaib Azeem, Joaquín Soriano-López, Isaac Brotons-Alcázar, Christopher Allen, Ramón Torres-Cavanillas, Roger Sanchis-Gual, Eugenio Coronado

{"title":"Design of Core@Shell Nanoparticles Based on Gold and Magnetic NiFe Prussian-Blue Analogues Featuring Shape-Dependent Magnetic and Electrochemical Activity","authors":"Shoaib Azeem, Joaquín Soriano-López, Isaac Brotons-Alcázar, Christopher Allen, Ramón Torres-Cavanillas, Roger Sanchis-Gual, Eugenio Coronado","doi":"10.1021/acs.inorgchem.4c05320","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.4c05320","url":null,"abstract":"Au@Prussian-Blue analogue (PBA) core@shell nanoparticles (NPs) are highly versatile nanostructures with complementary and shape-dependent properties of interest in the current technologies. However, due to the high reactivity of cyanides toward Au, scarce PBAs have been successfully synthesized in direct contact with Au NPs, leaving the formation of anisotropic Au@PBA NPs as a significant synthetic challenge. Here, we have developed a robust protocol for synthesizing core@shell NPs, composed of a magnetic CsNi[Fe(CN)6] PBA shell grown on individual Au NPs, regardless of the core morphology (spheres, rods, or stars). Specifically, the uniqueness of our protocol lies in the prior Au core functionalization with anchoring molecules that facilitate PBA growth while preventing Au etching and preserving the initial oxidation states of the metals. This has afforded direct growth of ferromagnetic NiIIFeIII PBAs on Au NPs. Moreover, by exploiting the structural mismatch at the Au/PBA interface and the curvature of anisotropic Au templates, we manage to induce a substantial structural strain within the PBA shell. When star-shaped Au nanoparticles are used, a maximum strain of 2.0% is reached. This strain combined with an increased polycrystallinity lead to modifications in the PBA catalytic properties, resulting in a 10-fold improvement in the intrinsic electrocatalytic activity.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"10 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713621","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