Inorganic Chemistry Frontiers最新文献

{"title":"Unexpected photo-induced oxidative cyclization and luminescence switching in molecular aggregates of two acylhydrazone-based Ir(III) complexes","authors":"Xin-Tong Lv, Xiao-Dong Liu, Zhiping Zhou, Deng-Ke Cao","doi":"10.1039/d5qi00527b","DOIUrl":"https://doi.org/10.1039/d5qi00527b","url":null,"abstract":"Two iridium complexes, namely [Ir(ppy)<small>₂</small>(mbpymbh)]PF<small>₆</small> (<strong>1</strong>) and [Ir(dfppy)<small>₂</small>(mbpymbh)]PF<small>₆</small> (<strong>2</strong>), exhibit unexpected photoreactivity, although the incorporated ligands ppyH, dfppyH and mbpymbh have no inherent photochemical activity. The molecular aggregates of <strong>1</strong> and <strong>2</strong>, formed in a CH<small>₃</small>CN–H<small>₂</small>O (v/v = 1/9) mixed solvent, show photo-induced luminescence switching, with the emission-color change from red to orange for <strong>1</strong>, while a transition from the off state to on state with an emission band at 566 nm for <strong>2</strong>. These changes in luminescence are assigned to photo-induced oxidative cyclization of the acylhydrazone units in <strong>1</strong> and <strong>2</strong>, thus generating photoproducts <strong>1-O</strong> and <strong>2-O</strong>. Complexes <strong>1-O</strong> and <strong>2-O</strong> were isolated and identified from their crystal structures. We discussed both the effect factors and the reaction mechanism of the photo-oxidation reactions for complexes <strong>1</strong> and <strong>2</strong>, as well as the luminescence properties of complexes <strong>1</strong>, <strong>2</strong>, <strong>1-O</strong> and <strong>2-O</strong>. The discovery of photo-induced oxidative cyclization in this work not only provides a new class of photo-responsive luminescent materials, but also offers a novel synthesis method for 1,3,4-oxadiazole-based Ir(<small>III</small>) complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143736779","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Toward high durable aqueous zinc ion batteries: A review of MOFs/MOF derived cathode materials","authors":"Yi Liu, Xiang Wu, Yoshio Bando","doi":"10.1039/d5qi00555h","DOIUrl":"https://doi.org/10.1039/d5qi00555h","url":null,"abstract":"The key to developing aqueous zinc ion batteries (AZIBs) is to design advanced cathodes that match well with zinc anode. Metal-organic framework (MOF)-based materials have emerged as a research focus due to their unique benefits in energy storage. However, researchers lack clear guidance on MOFs and their derived materials as AZIBs electrode materials, as well as a systematic exploration of their Zn2+ storage mechanisms. Herein, we summarize recent research progress in pristine MOFs and derivatives for high-performance AZIBs. Moreover, we provide a detailed understanding of the energy storage mechanisms. Finally, we propose the challenges and perspectives about MOFs and derivatives for next-generation aqueous energy devices. This review promotes insights into innovations in MOF-based cathode materials and provides inspiration for future efficient energy storage and conversion technologies.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"103 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143744738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Harnessing Metal Complexes to Target Tumour Bioenergetics and Metabolic Vulnerabilities","authors":"Muhammad Nafees, Fei He, Lili Feng, Muhammad Hanif, piaoping yang","doi":"10.1039/d5qi00168d","DOIUrl":"https://doi.org/10.1039/d5qi00168d","url":null,"abstract":"Metal-based complexes continue to be an exciting avenue in the quest for novel therapeutic approaches to treat malignant tumours. This is due to their versatile coordination chemistry, tunable redox activity, and distinct mechanisms of action. Cancer cells proliferate by adopting various metabolic pathways to fulfil their bioenergetic and biosynthetic demands. These altered metabolic pathways also contribute to substantial resistance to clinically approved drugs such as cisplatin. Therefore, designing therapeutic agents targeting specific metabolic pathways in tumours is a promising approach and has been widely explored in recent years. In this perspective, we provide a detailed mechanistic overview of the state-of-the-art progress of metal-based compounds that target cancer bioenergetics and various metabolic pathways to inhibit cancer progression. We also provide a comprehensive analysis of the most relevant metal complexes that concurrently target metabolic pathways and stimulate immunological response, thereby eliciting a synergistic effect that enhances treatment efficacy and overcomes drug resistance issues. Gaining insights into the structural features of these metal-based compounds will open a new therapeutic window to treat nasty tumours.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"101 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143734148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The impact of “empty-corner” tetrahedra in the synthesis of MFI type zeolites: unveiling selenium stereoactivity","authors":"Mishel Markovski, Abdallah Amedlous, Eddy Dib, Anna Kaleta, Francesco Dalena, Davide Salusso, Mathias Barreau, Diogenes Honorato Piva, Marco Giuseppe Geloso, Aymeric Magisson, Svetlana Mintova","doi":"10.1039/d5qi00567a","DOIUrl":"https://doi.org/10.1039/d5qi00567a","url":null,"abstract":"This study investigates the impact of selenium in different oxidation states, specifically Se<small>⁶⁺</small> and Se<small>⁴⁺</small>, on the structural features of MFI-type zeolites. Se<small>⁴⁺</small> is characterized by trigonal pyramidal coordination, forming a [Se<small>⁴⁺</small>O<small>₃</small>E]<small>²⁻</small> entity (E being an active lone pair of electrons). The three-coordinated [Se<small>⁴⁺</small>O<small>₃</small>E]<small>²⁻</small> entity represents an “empty-corner tetrahedron”, analogous to four-coordinated [Se<small>⁶⁺</small>O<small>₄</small>]<small>²⁻</small> and [SiO<small>₄</small>]<small>⁴⁻</small> tetrahedra. Aiming to understand the impact of lone pair bearing complexes on MFI, Se<small>⁴⁺</small> and Se<small>⁶⁺</small> were introduced through a one-pot synthesis approach giving rise to Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI samples. Both the Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI samples exhibit monoclinic symmetry at room temperature, transitioning into orthorhombic symmetry at temperatures above 100 °C and reverting to monoclinic symmetry upon cooling. A significant difference was observed in terms of the silanol content, <em>i.e.</em> Se(<small>IV</small>)-MFI shows a lower concentration of SiOH compared to Se(<small>VI</small>)-MFI. These observations are coherently supported by <small>²⁹</small>Si and <small>⁷⁷</small>Se NMR, Se K-edge XAS, FT-IR, and Raman spectroscopy, suggesting that Se<small>⁴⁺</small> oxycomplexes with a lone pair of electrons are more favorable for incorporation into the MFI framework compared to Se<small>⁶⁺</small>. <small>⁷⁷</small>Se NMR analyses revealed similar Se tetrahedral coordination in both Se(<small>VI</small>)-MFI and Se(<small>IV</small>)-MFI, indicating the stabilizing role <em>i.e.</em> oxidation of Se<small>⁴⁺</small> to Se<small>⁶⁺</small> directly during crystallization of MFI. Considering the differences in the silanol content and the similarities in Se coordination states in Se(<small>IV</small>)-MFI and Se(<small>VI</small>)-MFI, the transformation of “empty-corner tetrahedra” into regular tetrahedra <em>i.e.</em> selenite to selenate favors the introduction of Se in the MFI framework. These results provide valuable insights into the tunability of zeolite frameworks using selenium in different oxidation states.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723246","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Phosphole oxide-based cyclometalated platinum(II) β-diketonate complexes for cooperative self-assembly and solution-processable resistive memories with excellent stability","authors":"Andy Shun-Hoi Cheung, Eugene Yau-Hin Hong, Vivian Wing-Wah Yam","doi":"10.1039/d4qi03092c","DOIUrl":"https://doi.org/10.1039/d4qi03092c","url":null,"abstract":"A new class of neutral phosphole oxide-based cyclometalated platinum(<small>II</small>) β-diketonate complexes has been demonstrated to show cooperative self-assembly in THF–water mixtures, modulated by the directional Pt⋯Pt interactions along with π–π stacking and/or hydrophobic interactions. The phosphole oxide-based cyclometalating ligand has been found to play an important role in determining the morphologies of aggregates in THF–water mixtures. Moreover, platinum(<small>II</small>) complexes serving as active materials in resistive memory devices have been found to show promising binary memory performance with a low switching threshold voltage, long retention time and high ON/OFF ratio compared to devices based on reported organometallic complexes. The rich self-assembly and resistive memory properties of the complexes presented in the current work have illustrated the versatility of the robust platinum(<small>II</small>) complexes that could be utilized for the development of functional materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"22 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bulk Crystal Growth and Optical Properties of Novel Organic-inorganic Hybrid Nonlinear Optical Thiocyanate: [Mn(CH3CONH2)2] [Hg(SCN)4]","authors":"Peiqing Long, Chun-Li Hu, Xitao Liu, Jiang-Gao Mao","doi":"10.1039/d5qi00371g","DOIUrl":"https://doi.org/10.1039/d5qi00371g","url":null,"abstract":"The growth of bulk nonlinear optical (NLO) crystals that exhibit robust second harmonic generation (SHG) is currently an intriguing and rapidly advancing field for laser and photonic applications. Among the various options available, organic-inorganic hybrid materials offer numerous possibilities due to their distinctive amalgamation of inorganic coordinate frameworks and organic molecules. Herein, we have successfully developed a novel non-centrosymmetric (NCS) organic-inorganic hybrid NLO material, manganese mercury thiocyanate-bis(acetamide), [Mn(CH3CONH2)2][Hg(SCN)4] (MMTA), by synergistically incorporating inorganic polyhedra and organic conjugate molecules. The crystal displays a polar architecture comprising an asymmetric [HgS4] tetrahedron and [MnN4O2] octahedron which are connected by four π-conjugated -S-C≡N- ligands. More intriguingly, inch-size single crystals with dimensions up to 50×50×12 mm3, have been easily grown from aqueous solutions by temperature-lowering method. The optical properties investigation suggests that MMTA is a phase-matching NLO material with a large SHG response approximately 2.5 times that of KH2PO4, demonstrating its potential for NLO applications. Based on a combination of structural analysis and theoretical calculations, it is suggested that the significant SHG response can be attributed to the cooperative interaction between conjugated organic molecules and a highly asymmetric inorganic distorted octahedron. This work introduces an effective approach for the discovery of high-performance quadratic NLO materials, with a particular focus on organic-inorganic hybrid compounds.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143723290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Hydroxyl-Modified Fullerene C70(OH)8 Induces Pyroptosis for Cancer Therapy","authors":"Hang Zhang, Zhen Liu, Xiaofei Zhu, Jun-Long Zhang, Liangbing Gan","doi":"10.1039/d5qi00548e","DOIUrl":"https://doi.org/10.1039/d5qi00548e","url":null,"abstract":"Fullerene (C70), a promising new photosensitizer, has faced challenges in its biological applications due to its extreme hydrophobicity. In order to enhance the solubility of fullerene (C70) and facilitate its biological applications, we synthesized a novel hydroxyl-modified fullerene compound (C70(OH)8) with excellent photosensitizing properties. The introduction of hydroxyl groups allows it to self-assemble with DSPE-PEG(2000), therefore, we prepared its nanomedicines(C70(OH)8@NP). Under white light irradiation, C70(OH)8@NP stimulates the production of reactive oxygen species (ROS), Furthermore, results has demonstrated that a substantial amount of ROS can also be generated within cells, resulting in cell death. We found that C70(OH)8@NP can induce both apoptosis and pyroptosis in HeLa cells and identified its mechanism of cell death through the activation of Caspase 3/Gasdermin E pathways. Importantly, C70(OH)8@NP demonstrates significant anti-tumor activity in a nude mouse tumor-bearing model. These results highlight the potential of novel fullerene compounds as photodynamic therapy agents.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"125 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineering geometric metamorphosis in {P6M2Mo16O73}-based high-nuclearity metal superclusters: from tetrahedral to square assemblies via topological transformations","authors":"Xiaoyan Zhang, Hui Li, Na Xu, Xiaodong Liu, Xiu-Li Wang","doi":"10.1039/d5qi00460h","DOIUrl":"https://doi.org/10.1039/d5qi00460h","url":null,"abstract":"The synthesis of superclusters is vital for understanding their self-assembly mechanisms, requiring precise control over composition, orientation, and connectivity. The tenets of reticular chemistry afford a systematic approach to the architectural design and regulation of molecular entities, thereby enabling the fulfillment of preconceived structural objectives. Herein, the strategic introduction of transition metal ions, Co<small>^II</small> and Ni<small>^II</small>, has enabled the controlled formation of two novel closely related anionic superclusters based on the {Sr⊂P<small>₆</small>M<small>₂</small>Mo<small>₁₆</small>O<small>₇₃</small>} clusters: <strong>Co<small>₁₂</small>Sr<small>₄</small>Mo<small>₈₀</small>P<small>₃₆</small></strong> (<strong>1</strong>) and <strong>Na<small>₄</small>Ni<small>₂₃</small>Sr<small>₄</small>Mo<small>₈₈</small>P<small>₅₂</small></strong> (<strong>2</strong>). The former manifests a tetrahedral structure, while the latter, derived from topological transformations of cluster <strong>1</strong>, exhibits a unique square geometry. Structural elucidation revealed that the integration of Mo<small>^V</small> ions in a reduced state, in concert with distinct transition metal ions (Co<small>^II</small> and Ni<small>^II</small>), plays a pivotal role in determining the geometric profiles of these superclusters. Furthermore, clusters <strong>1</strong> and <strong>2</strong> demonstrate efficacy as heterogeneous catalysts, significantly promoting the transformation of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO).","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"41 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713341","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineered Molybdenum Disulfide-based Nanomaterials for Capacitive Deionization Application","authors":"Maiyong Zhu, Xinyue Xiang, Xinyao Jiang, Yu Yang, Kai Zhang","doi":"10.1039/d4qi03147d","DOIUrl":"https://doi.org/10.1039/d4qi03147d","url":null,"abstract":"Capacitive deionization (CDI) is a highly promising technique for removal ions from water, showing great perspective in desalination of salty water and wastewater remediation. CDI displays an energy efficiency, simple operation, excellent reversibility, long-term stability, and high feasibility for coupling with other techniques. Similar to supercapacitors, the electrode materials play crucial role in determining CDI performance, such as operating voltage, desalination capacity, and the lifecycle of CDI cells. Molybdenum disulfide (MoS2), a typical two-dimensional (2D) metal sulfide, has gained tremendous attention in CDI technique due to its exceptional mechanical, electrical, and optical properties. Herein, we critically reported deliberated the inventory and the recent progress in the rational design of MoS2 based electrodes for CDI cells. We start with a brief introduction to foundation knowledge of CDI system and structure of MoS2. To make the review comprehensive, we then summarized the available common techniques to prepare MoS2 based nanomaterials, spanning from various exfoliation processes, chemical vapor deposition, colloidal synthesis, hydrothermal/solvothermal synthesis, and molten salt synthesis. Significantly, the recent progress of MoS2 based electrodes in CDI application is summarized in detail. These systems are divided into pristine MoS2 and various MoS2 based composite with other species, such as carbon, conducting polymer, metal oxide, MXene, and C3N4. For assisting further development of MoS2 electrodes for efficient and long-term stable CDI, some challenges and possible solutions are outlined.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"34 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intensified ion-to-channel interactions within pyridinic covalent organic framework membranes towards exclusive lithium-ion sieving","authors":"Weihao Yu, Yijun Qian, Haoqing Ji, Zebin Zhu, Tong Wu, Tao Qian, Chenglin Yan, Jianmei Lu","doi":"10.1039/d5qi00062a","DOIUrl":"https://doi.org/10.1039/d5qi00062a","url":null,"abstract":"Membrane separation technologies demonstrate outstanding potential for achieving efficient lithium-ion (Li<small>⁺</small>) extraction from the battery leachate in a high-value and eco-friendly way, but, up to date, the rare focuses on developing one kind of specific Li<small>⁺</small>-filter applicable in this context. Herein, we prepared a pyridinic two-dimensional covalent organic framework (2D COF-Py) membrane featuring non-angstrom-sized 1D channels for exclusive Li<small>⁺</small> sieving. The 2D COF-Py membrane enabled an excellent Li<small>⁺</small> permeance (∼30 mmol m<small>⁻²</small> h<small>⁻¹</small>) with impressive Li<small>⁺</small>/M<small>²⁺</small> selectivity of over 47 under any mixed salt conditions (<em>e.g.</em> LiCl-CoCl<small>₂</small>, LiCl-NiCl<small>₂</small>, and LiCl-MnCl<small>₂</small>). The experimental measurements and theoretical calculations revealed the dual roles of pyridine groups in dominating the ion transport behavior across the COF membrane. One role was to ensure fast Li<small>⁺</small> transmembrane activity <em>via</em> electrostatic attraction and the other was to suppress M<small>²⁺</small> free diffusion by forming strong coordination interactions. When stimulated battery leachate (a quaternary cation solution) was used as the feed solution, the COF-Py membrane not only sustained a striking separation performance under a long-term operation test without losing any trade-off but also maintained structural stability under high-salinity conditions.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"33 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713339","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}