Inorganic Chemistry最新文献_第2页

Zirconium Metal–Organic Frameworks as Micromotors with Enzyme-like Activity for Glutathione Detection

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-28 DOI: 10.1021/acs.inorgchem.5c00494

Xiaoqing Li, Gui Wang, Dongyang Zhou, Ziwei Lan, Fengling Jiang, Dickon H. L. Ng, Jia Li

引用次数: 0

Local Electronic Regulation by Oxygen Coordination with Single- Atomic Iridium on Ultrathin Cobalt Hydroxide Nanosheets for Electrocatalytic Oxygen Evolution

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.5c00659

Youkui Zhang, Yujuan Pu, Wenhao Li, Yunxiang Lin, Haoyuan Li, Yingshuo Wu, Tao Duan

{"title":"Local Electronic Regulation by Oxygen Coordination with Single- Atomic Iridium on Ultrathin Cobalt Hydroxide Nanosheets for Electrocatalytic Oxygen Evolution","authors":"Youkui Zhang, Yujuan Pu, Wenhao Li, Yunxiang Lin, Haoyuan Li, Yingshuo Wu, Tao Duan","doi":"10.1021/acs.inorgchem.5c00659","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00659","url":null,"abstract":"Rationally optimizing the atomic and electronic structure of electrocatalysts is an effective strategy to improve the activity of the electrocatalytic oxygen evolution reaction (OER), yet it remains challenging. In this work, atomic heterointerface engineering is developed to accelerate OER by decorating iridium atoms on low-crystalline cobalt hydroxide nanosheets (Ir–Co(OH)x) via oxygen-coordinated bonds to modulate the local electronic structure. Leveraging detailed spectroscopic characterizations, the Ir species were proved to promote charge transfer through Ir–O–Co coordination between the Ir atom and the Co(OH)x support. As a result, the optimized Ir–Co(OH)x exhibits excellent electrocatalytic OER activity with a low overpotential of 251 mV to drive 10 mA cm–2, which is 63 mV lower than that of pristine Co(OH)x. The experimental results and density functional theory calculations reveal that the isolated Ir atoms can regulate the local coordination environment and electronic configuration of Co(OH)x, thus accelerating the catalytic OER kinetics. This work provides an atomistic strategy for the electronic modulation of metal active sites in the design of high-performance electrocatalysts.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713620","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

Halogen-Driven Spin Dynamics: Exploring Correlation of Cooperativity and Spin Crossover in Solid-State Mononuclear Fe(III) Schiff-Base Complexes

IF 4.6 2区化学

Inorganic Chemistry Pub Date : 2025-03-27 DOI: 10.1021/acs.inorgchem.5c00885

Li-Wen Chen, Hai Zhu, Hua-Wei Zhou, Hao-Zhe Zhang, Sheng-Ze Zhao, Yong-Hua Li, Shi Wang

{"title":"Halogen-Driven Spin Dynamics: Exploring Correlation of Cooperativity and Spin Crossover in Solid-State Mononuclear Fe(III) Schiff-Base Complexes","authors":"Li-Wen Chen, Hai Zhu, Hua-Wei Zhou, Hao-Zhe Zhang, Sheng-Ze Zhao, Yong-Hua Li, Shi Wang","doi":"10.1021/acs.inorgchem.5c00885","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c00885","url":null,"abstract":"We report the synthesis, crystal structures, and magnetic properties of four new mononuclear iron(III) complexes, [Fe(5-X-sal2trien)]ReO4 (X = F (1); X= Cl (2); X = Br (3); X = I (4)), where (5-X-sal2trien)2– is a halogen-substituted hexadentate Schiff-base (N4O2)2– ligand. Magnetic susceptibility measurements demonstrated that complex 1 maintains a high-spin (HS) state, while complexes 3 and 4 display a very gradual spin crossover (SCO) above 300 K. Complex 2 exhibits a unique two-step thermo-induced spin-state switching at T1/2 = 250 K (1) and 209 K (2) with symmetry breakings. Single-crystal X-ray structures of 2 are obtained at 300, 250, and 100 K, respectively, indicating two structural phase transitions (Pccn–Pmmn–P21/m). The introduction of halogen substituents on (sal2trien)2– ligands has a great influence on cooperativity and finally the magnetic properties of Fe(III) SCO complexes.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"183 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723837","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

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