Inorganic Chemistry Frontiers最新文献

{"title":"Transformable Cis-trans Isomerism of Ruthenium (II) Complexes with Photoactivated Anticancer Activity","authors":"Chen Pan, Pui-Yu Ho, Wan-Qiong Huang, Gui-Feng Huang, Li-Hua Zhang, Daniel Nnaemaka Tritton, Shek-Man Yiu, Wai-Lun Man, Chi-Chiu Ko, Chi-Fai Leung, Wen-Xiu Ni","doi":"10.1039/d4qi02665a","DOIUrl":"https://doi.org/10.1039/d4qi02665a","url":null,"abstract":"Photoactivated chemotherapy (PACT) provides a new alternative cancer treatment strategy compared to conventional therapy. In this study, a series of diisocyano ruthenium (II) complexes Ru(PBO)2(RNC)2 containing 2-benzoxazol-2-ylphenolate (PBO) auxiliary ligand and their potential application as PACT agents are reported. The complexes exhibit two geometric isomers, i.e., trans, trans, trans (T1 – T3) and cis, trans, cis (C1 – C3) forms. Although C1 – C3 show minimal cytotoxicity (IC50 = 60.1 to >100 μM) toward various cancer cells in the dark, the corresponding T1 – T3 complexes exhibit much stronger cytotoxic effects (IC50 = 3.7 – 39.4 μM). C1 can be readily photoconverted into T1 upon visible-light irradiation (white light), as shown by UV/Vis and 1H NMR. The increased toxicity of the T-form is partially attributed to its reaction with glutathione, in contrast to the C-form analogue. The anticancer activities of T1 were studied in vitro and in vivo. This is the first study that demonstrates the photoisomerization of isocyano ruthenium(II) complex Ru(PBO)2(CNR)2 as an attractive approach for anticancer PACT agent.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"47 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968556","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":"Deep-ultraviolet sulfamate halides with halogen-centered secondary building units for enhanced optical anisotropy","authors":"Xuefei Wang, Qingwen Zhu, Yunseung Kuk, Hongheng Chen, Qi Wu, Qun Jing, Kang Min Ok","doi":"10.1039/d4qi03302g","DOIUrl":"https://doi.org/10.1039/d4qi03302g","url":null,"abstract":"The insufficient birefringence of non-π-conjugated optical materials presents a significant challenge for their deep-ultraviolet (DUV) applications. In this work, four DUV sulfamate halide co-crystals, AX(NH3SO3) (A = Rb, Cs; X = Cl, Br), were successfully synthesized through functional chromophore engineering. All four compounds exhibit promising DUV transparent windows, with RbCl(NH3SO3) and CsCl(NH3SO3) demonstrating short DUV cut-off edges below 185 nm. Remarkably, a significant improvement in birefringence, ranging from 0.069 to 0.075, was observed in all four crystals. These values represent the highest birefringence observed for non-π-conjugated DUV optical materials and exhibit optical anisotropy comparable to that of DUV materials containing π-conjugated groups. Theoretical analysis using the real-space atom-cutting method reveals that the [XAm] (X = Cl, Br; A = Rb, Cs) secondary building units (SBUs) contribute significantly to the birefringence. The incorporation of halogen-centered chromophores provides a novel strategy for designing non-π-conjugated DUV materials with enhanced birefringence and phase-matching capabilities.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"137 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975334","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":"Fluorescence Lifetime Imaging-Guided Photodynamic Therapy over Two-Photon Responsive Metal-Organic Frameworks","authors":"Bo Li, Xin Lu, Xianshun Sun, Yupeng Tian, Zijuan Hai, Dandan Li, Hong-Ping Zhou","doi":"10.1039/d4qi03014a","DOIUrl":"https://doi.org/10.1039/d4qi03014a","url":null,"abstract":"In the realm of photodynamic therapy (PDT), the incorporation of real-time feedback through two-photon fluorescence lifetime imaging poses a significant challenge, primarily due to the intricate nature of photosensitizer design. In our investigation, we have effectively constructed a versatile platform labeled as ZTBH using a post-ligand modification approach, resulting in enhanced two-photon fluorescence capabilities and notable responsiveness of fluorescence lifetime to variations in the cellular microenvironment. The distinctive synergy between intersystem crossing and linker-to-cluster charge transfer within ZTBH empowers the generation of ample reactive oxygen species (1O2 and O2•-), thereby yielding remarkable efficiency in PDT. Moreover, the capping of hyaluronic acid (HA) through coordination method confers ZTBH with cancer-specific targeting properties. Subsequently, with the aid of a two-photon fluorescence lifetime imaging microscope (TP-FLIM), ZTBH not only achieves successful two-photon photodynamic therapy but also enables real-time visualization of cellular microenvironment changes throughout the apoptosis process. This investigation underscores a viable approach in the creation of two-photon fluorescence lifetime photosensitizers for visualizing the PDT procedure.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"36 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961542","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":"Strategic design of vacancies and phase in flexible MoS2 for boosting triiodide reduction performance","authors":"Xu Cai, Xuan Wang, Bixue Sun, Chenzhao Yang, Mingzhu Chen, Shuang Lu, Yinglin Wang, Xintong Zhang","doi":"10.1039/d4qi02986k","DOIUrl":"https://doi.org/10.1039/d4qi02986k","url":null,"abstract":"Developing low-cost, efficient and flexible electrocatalysts is an important approach to promote the commercial development of dye-sensitized solar cells (DSSCs). Herein, we utilize a simple and mild H2O2 etching strategy to introduce Mo vacancies on the surface of MoS2 thin film and cause the crystal phase change from 2H to 1T. By systematically adjusting the etching time, temperature, and solution concentration, the optimal concentration of Mo vacancies was obtained. As a result, the optimized flexible CE (MoS2-60 s) exhibited the highest power conversion efficiency (4.45%), which was increased by 33.24% compared to the untreated MoS2 sample. Meanwhile, the PCE of MoS2-60 s CE under simulated indoor light irradiation (1000 lux) was 24.33%, demonstrating its advantages for indoor PV applications. The above data proved the effectiveness of the strategy about regulating vacancy and phase induced by etching, especially in indoor low light environment. Furthermore, the prepared flexible MoS2-60 s CE also possessed prominent electrochemical stability, bending durability and uniform electrocatalytic activity with the size of 4.5 × 5 cm. The significantly enhanced effect is mainly attributed to the synergistic effect of Mo vacancy and phase. Moreover, the transmittance of MoS2 CE after etching has been significantly improved, which has the potential for application in transparent DSSCs. In this article, the CE with high response in simulated indoor light, good stability, flexibility and transparency was prepared, which expanded the application scenario of DSSCs and promoted its commercial application.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"86 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961544","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":"Recent advances in computational modelling of mononuclear actinide single molecule magnets†","authors":"Sourav Dey and José J. Baldoví","doi":"10.1039/D4QI02326A","DOIUrl":"10.1039/D4QI02326A","url":null,"abstract":"<p >Significant progress has been made in lanthanide-based single mononuclear SMMs in the past two decades, raising their magnetic memories to liquid nitrogen temperature. On the other hand, a handful of actinide-based mononuclear SMMs, primarily based on uranium, have been reported. Among the advantages of actinides over lanthanides are their more significant spin–orbit coupling and stronger metal–ligand covalency, which make them better candidates for providing mononuclear SMMs with high energy barriers. However, the lack of design criteria based on theoretical studies and their more challenging experimental preparation has led to limited results that are still distant from their promising potential. Recently, there has been an increasing interest in their <em>ab initio</em> modelling to understand their electronic structure and magnetic properties. This has led to setting up the first steps regarding their chemical design, thus opening new possibilities for improvement in the near future. In this review, we focus on these recent works and rationalise how far the field has come forward, exploring the potential of designing an advanced generation of actinide mononuclear SMMs.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 4","pages":" 1349-1370"},"PeriodicalIF":6.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qi/d4qi02326a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940073","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A novel benzothiazole-1,2,3-triazole-based arene osmium(ii) complex as an effective rhabdomyosarcoma cancer stem cell agent†","authors":"Sofia Sharkawy, Alba Hernández-García, Hana Kostrhunova, Delia Bautista, Lenka Markova, María Dolores Santana, Jana Kasparkova, Viktor Brabec and José Ruiz","doi":"10.1039/D4QI02737J","DOIUrl":"10.1039/D4QI02737J","url":null,"abstract":"<p >We designed a series of pseudo-octahedral arene Os(<small>II</small>) complexes (<strong>Os1–Os5</strong>) with the general formula [(η<small>⁶</small>-<em>p</em>-cym)Os(BTAT)Cl]<small>⁺</small>, where BTAT represents chelating N^N′ ligands based on the 1-aryl-4-benzothiazolyl-1,2,3-triazole scaffold. The structures of <strong>Os3</strong> and <strong>Os5</strong> were confirmed by X-ray diffraction, and <strong>Os5</strong> exhibits a bathochromic shift in its absorption band compared to the other complexes, likely due to the electron-donating properties of the substituent NMe<small>₂</small>. <strong>Os5</strong> also hydrolyzed without losing its BTAT ligand and exhibited the highest cellular accumulation in Rhabdomyosarcoma (RD) cancer cells. The investigated Os(<small>II</small>) complexes demonstrated moderate antiproliferative activity across six cancer cell lines, with <strong>Os5</strong> being the most potent, showing activity comparable to or better than conventional cisplatin. Cellular accumulation was a key factor influencing their antiproliferative effect, though binding to human serum albumin did not play a significant role. Further studies with <strong>Os5</strong> in RD cells, the most responsive cell line, revealed that its mechanism of action includes mitochondrial dysfunction, apoptosis <em>via</em> a caspase-dependent pathway, and cell cycle arrest at the G1 phase. <strong>Os5</strong> also increased the production/generation of reactive oxygen species (ROS) in RD cells, implicating ROS production as a contributor to its activity. Importantly, <strong>Os5</strong> was effective against cancer stem cells (CSCs) in 3D spheroid models, marking the first report of an osmium-based compound targeting CSC-enriched RD cells. This highlights the potential of <strong>Os5</strong> as a CSC-targeted therapy, addressing the need for treatments that prevent relapse and metastasis. The study underscores the promising role of metal-based complexes in cancer stem cell chemotherapy.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 4","pages":" 1693-1715"},"PeriodicalIF":6.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qi/d4qi02737j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940076","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Crystallization induces thermally activated delayed fluorescence of Ag14 nanoclusters†","authors":"Jin-Sen Yang, Lu-Yao Xiao, Fan Liu, Jun Xu, Xi-Yan Dong, Jia-Hua Hu, Jing Li and Shuang-Quan Zang","doi":"10.1039/D4QI02920H","DOIUrl":"10.1039/D4QI02920H","url":null,"abstract":"<p >Studying the differences in the excitonic dynamic processes between the dispersed state and crystalline state is important for understanding crystallization-induced emission enhancement (CIEE). In this work, we characterized the photophysical processes of Ag<small>₁₄</small> nanoclusters both in solution and in the crystalline state using photoluminescence spectra combined with transient absorption spectra. The nanoclusters exhibit fluorescence (Fl)–phosphorescence (Ph) co-dominant emission in solution, while thermally activated delayed fluorescence (TADF) is observed in the crystals. From solution to crystals, the photoluminescence quantum yield (PLQY) of the cluster improves from below 0.1% to 33% due to the boosting of TADF combined with the restriction of intramolecular motion (RIM) and the aggregation-induced barrier to oxygen (AIBO). We reveal that the enhanced TADF of crystalline samples of Ag<small>₁₄</small>-dcbdt can be attributed to inter-cluster electron orbital coupling, which decreases the singlet–triplet splitting energy. These findings provide new insights into the CIEE of cluster-based aggregates and can be used to guide the synthesis of high-performance cluster-based luminescent materials.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 4","pages":" 1420-1426"},"PeriodicalIF":6.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940085","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":"Praseodymium-selenium connecting selenotungstate containing mixed building blocks for catalytic synthesis of aza-heterocycles","authors":"Guo-Ping Yang, Jiawei Cao, Zhoufu Lin, Shi-Xiong Li, Yayu Dong, Yufeng Liu","doi":"10.1039/d4qi02897j","DOIUrl":"https://doi.org/10.1039/d4qi02897j","url":null,"abstract":"A novel praseodymium-selenium connecting selenotungstates [Pr2.5(SeO)(SeO3)0.25(mal)(W4O9)(SeW8O32)(SeW9O33)2(H2O)4]16- (BC-Pr) (H3mal = DL-malic acid) was synthesized in acidic aqueous solution. The skeleton of BC-Pr is formed by two {SeW9} and one {SeW8} building blocks encapsulating a {Pr2Se2W4(mal)} unit. Two adjacent trimers are bridged by Pr3+, {SeO3} and mal to construct a hexamer that is alternately connected through Pr-O-W bonds to form one-dimensional chains. Its remarkable structural feature lies in its inclusion of two building block types and selenium acts as both heteroatom and linkage, which are extremely rare in selenotungstates chemistry. In addition, BC-Pr exhibits excellent catalytic activity for the cyclization of 2-aminobenzamides/2-aminobenzenesulphonamides with aldehydes under green and mild conditions, leading to the synthesis of a series of 2,3-dihydroquinazolinones and 3,4-dihydro-2H-1,2,4-benzothiadiazine-1,1-dioxides with high yields. The present study provides comprehensive insights into the novel fabrication of lanthanide-substituted POMs and their immense potential in environmentally friendly synthesis of aza-heterocycles.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"75 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142940136","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":"A new fluorescent oxaliplatin(iv) complex with EGFR-inhibiting properties for the treatment of drug-resistant cancer cells†","authors":"Monika Caban, Philipp Fronik, Alessio Terenzi, Anja Federa, Julia H. Bormio Nunes, Rastislav Pitek, Dominik Kirchhofer, Hemma H. Schueffl, Walter Berger, Bernhard K. Keppler, Christian R. Kowol and Petra Heffeter","doi":"10.1039/D4QI03025G","DOIUrl":"10.1039/D4QI03025G","url":null,"abstract":"<p >Platinum chemotherapy is part of every second anticancer treatment regimen. However, its application is limited by severe side effects and drug resistance. The combination of platinum-based chemotherapeutics with EGFR inhibitors has shown remarkable synergism in clinical treatment. To enhance the tolerability of this combination, we designed a novel multi-action oxaliplatin-based platinum(<small>IV</small>) complex with an EGFR-inhibiting moiety (KP2749). KP2749 releases two independent cytotoxic agents upon reduction: oxaliplatin and the EGFR inhibitor KP2187, which was selected for its strong intrinsic fluorescence that became quenched upon complexation to metal ions. In particular, KP2749 demonstrated high stability and specific KP2187 release, with quenched fluorescent properties in its intact form, facilitating the investigation of its intracellular reduction. Notably, by exploiting its fluorescence, we demonstrated that intact KP2749 itself exhibited EGFR-inhibitory properties. Furthermore, subsequent experiments indicated that our complex was able to overcome resistance to oxaliplatin and EGFR inhibitors <em>in vitro</em> and in xenograft models <em>in vivo</em>. These effects were not only based on EGFR inhibition and DNA damage, but also improved cellular drug uptake. Finally, <em>in silico</em> docking analysis confirmed that the intact KP2749 complex had EGFR-binding properties, which were different from free KP2187. Consequently, these data suggested that the coordination of EGFR inhibitors to metal cores (like platinum) allow the fine-tuning of their EGFR-targeting properties. In conclusion, this study not only presents a new potential anticancer drug but also offers a novel fluorescent tool to study the intracellular drug release kinetics of platinum(<small>IV</small>) complexes.</p>","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":" 4","pages":" 1538-1552"},"PeriodicalIF":6.1,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/qi/d4qi03025g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ca2La(MS4)(BS3) (M = Ge/Si and Sn/Si): High performance infrared nonlinear optical materials designed by atomic site co-occupancy strategy","authors":"Ya-Xiang Han, Chun-Li Hu, Jiang-Gao Mao","doi":"10.1039/d4qi03060e","DOIUrl":"https://doi.org/10.1039/d4qi03060e","url":null,"abstract":"Exploration of new material systems and optical performance enhancement are huge challenges during the study of infrared nonlinear optical (IR NLO) materials. In this work, the first thioborate-thiogermanate and thioborate-thiostannate, Ca2La(Ge0.72Si0.28S4)(BS3) and Ca2La(Sn0.75Si0.25S4)(BS3), containing both co-occupied Ca2+/La3+ cation and [Ge/SiS4]4- or [Sn/SiS4]4-anion sites, have been designed through an atomic site co-occupancy strategy. They inherited favourable 3D network structures in which the effectively aligned [MS4]4- and [BS3]3- functional anions are bridged by Ca2+/La3+ cations. Remarkably, the title compounds achieved excellent IR NLO properties, including good chemical and thermal stabilities, wide light transmission ranges (0.45-11 μm), strong second harmonic generation responses (1.5 and 2.0 times that of commercial AgGaS2 at 2.05 µm) and high laser induced damage thresholds (7 and 6 times that of AgGaS2). Theoretical calculation and experimental results revealed that, on the basis of excellent structural framework, introducing more active functional groups through atomic site co-occupancy can simultaneously enhance the second harmonic generation effect and maintain a relatively high laser induced damage threshold. This work not only offers an easier synthetic route for mixed anionic thioborates, but also provides inspiration for the design of well-performed NLO materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"48 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937120","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}