Inorganic Chemistry Frontiers最新文献

{"title":"Exploring the photophysics and excited state reactivity of [Ru(4,4′-BTFMB)2 (L)]2+ complexes (L = bpy, phen, TAP) as photodynamic therapy agents: a theoretical investigation","authors":"Sandy Veríssimo Morais Quintão, Aline de Souza Bozzi, Willian Ricardo Rocha","doi":"10.1039/d5qi00077g","DOIUrl":"https://doi.org/10.1039/d5qi00077g","url":null,"abstract":"In this work, we explore the excited states of three different [Ru(4,4′-BTFMB)<small>₂</small> (L)]<small>²⁺</small> complexes (<strong>C1</strong>: L = bpy (2,2′-bipyridine); <strong>C2</strong>: L = phen (1,10-phenantroline); and <strong>C3</strong>: L = TAP (1,4,5,8-tetraazaphenanthrene)), aiming to investigate the ligand effects on their photophysical and photochemical properties and also to evaluate their suitability as photosensitizers (PS) for photodynamic therapy (PDT). Compound <strong>C3</strong> is a new theoretical proposition for which we have observed a significant lowering in the HOMO and LUMO energies, which can be interpreted as an extra stabilization of the complex, a highly desirable feature for a PS candidate. Also, the low-lying excited states showed a shift in the MLCT transition nature from <img align=\"middle\" alt=\"Image ID:d5qi00077g-t1.gif\" src=\"https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/QI/D5QI00077G/d5qi00077g-t1.gif\"/> to <img align=\"middle\" alt=\"Image ID:d5qi00077g-t2.gif\" src=\"https://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/Articleimage/2025/QI/D5QI00077G/d5qi00077g-t2.gif\"/>, confirming that the presence of a more electronegative atom in the third ligand lowers the energy of the orbitals due to a more effective π-backbonding. Furthermore, the investigation of the excited state reactions has shown a dual character possibility for the three complexes, being thermodynamically favorable for photosensitizing molecular oxygen through energy transfer and oxidizing guanosine-monophosphate through electron transfer. Complex <strong>C3</strong> presented the best reaction free-energy profile, indicating that this new compound is most suitable for use as a photosensitizer in PDT.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"57 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806311","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 Timeless Relevance of Size-Match Selectivity in Macrocyclic Fe(III) Complexes","authors":"Sara Camorali, Alessandro Nucera, Marco Saccone, Fabio Carniato, Mauro Botta, Francesco Blasi, Zsolt Baranyai, Lorenzo Tei","doi":"10.1039/d5qi00431d","DOIUrl":"https://doi.org/10.1039/d5qi00431d","url":null,"abstract":"Given the recent emergence of Fe(III) complexes as promising MRI contrast agents, significant interest has grown in understanding their coordination chemistry, particularly the delicate balance between thermodynamic and redox stability, kinetic inertness, and efficient relaxation enhancement. Among the most widely employed macrocyclic systems for Fe(III) coordination is functionalized 1,4,7-triazacyclononane (TACN). However, it is well-established that the small Fe(III) ion exhibits a preference for 6-membered chelate rings and, consequently, larger distances between macrocyclic N-donors to form stable complexes. In this work, we present a comprehensive investigation into the thermodynamic and redox stability, dissociation kinetics, and 1H relaxivity of four Fe(III) complexes. These feature hexadentate triacetate ligands derived from triazamacrocycles with ring sizes ranging from 9- to 12-membered, allowing us to systematically evaluate the impact of increasing the macrocyclic cavity size. The experimental results were subsequently validated through computational analysis. Employing Quantum Theory of Atoms in Molecules and the Interaction Region Indicator, we evaluated the shape, volumes, and intramolecular interactions within the four Fe(III) complexes. A key finding revealed that the stability of the Fe(III) complexes peaks with the ligand derived from the 11-membered ring, indicating optimal accommodation of the small Fe(III) ion. However, the most kinetically inert complex was observed with the 12-membered ring ligand. Conversely, relaxivity exhibited an opposite trend, decreasing with increasing ring size. This trend is attributed to variations in electronic parameters. Notably, none of the complexes exhibited a coordinated water molecule, resulting in inherently low relaxivity.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"8 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806313","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":"Achieving multifunctional MOF/polymer-based quasi-solid electrolytes via functional molecule encapsulation in MOFs","authors":"Xu Li, Hongwei Pan, Guijie Yin, Yang Xiang, Xitao Lin, Zhu Liu, Yinzhu Jiang, Qun Hui, Xuan Zhang, Maowen Xu","doi":"10.1039/d5qi00052a","DOIUrl":"https://doi.org/10.1039/d5qi00052a","url":null,"abstract":"The simultaneous realization of high safety and high electrochemical performance of quasi-solid-state electrolytes (QSSEs) has been challenging to accomplish since decades. Herein, a flame retardant-encapsulated metal–organic framework (MOFs) was incorporated as a filler into a poly(vinylidene fluoride-<em>co</em>-hexafluoropropylene) (PVDF-HFP) QSSE, addressing its safety concerns and enhancing the electrochemical performance. Notably, the mechanical properties and electrochemical performance of PVDF-HFP QSSE were improved by the introduction of UiO-66 fillers. As the flame retardant was trapped in the channels of MOFs, this approach effectively prevented side reactions arising from it. Moreover, the introduction of the flame retardant hexachlorocyclotriphosphazene (HCCP) modulated the electronic distribution characteristics within the channels of UiO-66 and reduced the zeta potential of UiO-66, thereby further enhancing the performance of the QSSE. The resultant QSSEs (PHU-QSSE) remained intact at 180 °C and exhibited excellent self-quenching characteristics. The flame retardant-encapsulated UiO-66 filler boosted the ionic conductivity of the PVDF-HFP electrolyte from 3.1 × 10<small>⁻⁴</small> S cm<small>⁻¹</small> to 6.9 × 10<small>⁻⁴</small> S cm<small>⁻¹</small> and elevated the Li<small>⁺</small> transfer number of the electrolyte from 0.27 to 0.59. At a current density of 0.5 mA cm<small>⁻²</small>, a lithium symmetric battery based on PHU-QSSE maintained a stable cycling for over 2500 hours, 15 times longer than those of PVDF-HFP electrolytes. When PHU-QSSE was paired with a LiFePO<small>₄</small> cathode, it showed a high capacity of 156 mA h g<small>⁻¹</small> at 1 C, exhibiting outstanding rate performance and maintaining 84.6% capacity after 500 cycles. This work not only provides a new pathway to solve the dilemma between safety and high electrochemical performance of QSSEs but also proves that the modification of MOF channels could provide more possibilities for future solid battery designs.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"28 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797724","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":"Materials Innovation in Scintillators for X-ray Detection","authors":"Kuilin Li, Wenqing Li, Qi Nie, Xiao Luo","doi":"10.1039/d5qi00671f","DOIUrl":"https://doi.org/10.1039/d5qi00671f","url":null,"abstract":"Since their introduction in the early 20th century, scintillators have become essential components in a wide range of applications, including high-energy physics, medical imaging, cryptography, and nuclear detection. As the demand for high-performance scintillating materials continues to rise in particle physics experiments and medical imaging technologies, the development of novel scintillator materials has become a critical area of research. In recent years, advancements in scintillators have flourished, presenting new opportunities for practical applications. This review presents a comprehensive overview of standard performance parameters for scintillators, aimed at enhancing understanding and evaluation of their advancements. We highlight the latest developments in scintillator materials, emphasizing research from the past three years and focusing on their intrinsic properties. Our analysis includes perovskite scintillators, nanoclusters scintillators as well as those doped with rare-earth ions, organic scintillators and the scintillators along with specialized structures. This classification offers a scientific perspective on the overall progress in the field of scintillators, and several forward-looking insights into the future development of scintillators were proposed, employing a problem-oriented approach. Eventually, we discuss the challenges encountered in scintillator development, explore future prospects, and provide valuable insights for improving their performances and expanding their applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"59 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797852","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":"Tailoring High Entropy Borides for Hydrogenation: Crystal Morphology and Catalytic Pathways","authors":"Abraham Rosenberg, Daniel T Lintz, Juncheng Li, Yiren Zhang, Joseph Doane, Miranda N Bristol, Alma Kolakji, Ting Wang, Michael Tyrone Yeung","doi":"10.1039/d5qi00311c","DOIUrl":"https://doi.org/10.1039/d5qi00311c","url":null,"abstract":"The high entropy boride (HEB) Al0.2Nb0.2Pt0.2Ta0.2Ti0.2B2, with its unique crystal structure and high coordination (platinum coordinated to 12 borons), has been shown in our previous work to exhibit exceptional catalytic properties, especially in sulfur-rich environments, where traditional platinum catalysts would succumb to sulfur-poisoning. In this work, we investigate the mechanism of the HEB catalyst, first by comparing the synthesis by flux growth, as previously reported, to an arc melted preparation. It is evident that the aluminum flux growth synthesis encourages the growth of single crystals, with clear and defined crystal facets, whereas the arc melted sample results in poorly defined facets with non-uniform morphology. Here, we explore two potential mechanisms: hydrogen spillover effect (HSPE) and hydrogen atom transfer (HAT) by which the catalytic pathway is performed. Hydrogenation reactions were performed using WO3 and 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO), which highlight the ability of the heterogeneous HEB catalyst to perform the hydrogenation through a suspended solid solution in addition to a dissolved solution. We propose that the HEB Al0.2Nb0.2Pt0.2Ta0.2Ti0.2B2 goes through a hybrid HAT/HSPE mechanism, where H2 bonds to the platinum atoms on the edges of the HEB, dissociate, then the radical hydrogen departs to the substrate.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806310","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":"Interfacial defect engineering to boost deep-ultraviolet photodetection based on a wide bandgap semiconductor heterostructure","authors":"Han Wu, Lincong Shu, Sihan Yan, Shulin Sha, Qing-Hua Zhang, Zeng Liu, Shan Li, Weihua Tang, Yuehui Wang, Jiaying Shen, Zhenping Wu, Kun Lin, Qiang Li, Jun Miao, Xianran Xing","doi":"10.1039/d5qi00691k","DOIUrl":"https://doi.org/10.1039/d5qi00691k","url":null,"abstract":"Wide bandgap semiconductors have emerged as a valuable class of deep-ultraviolet sensitive materials, showing great potential for next-generation integrated devices. Yet, to achieve a high performance of deep-ultraviolet detector without complicated designs at low supply voltage and weak light intensity has proven challenging. Herein, we design a new way to fabricate an ultrasensitive vertical-structured Ga2O3 photodetector with epitaxial oxygen-vacancy-rich In2O3 as the bottom conductive layer, realizing the detection to a rare weak deep UV light intensity (0.1 μW/cm²) at a voltage below 5 V, and demonstrating a surge in responsivity (36 A/W at -4.8 V and 2.2 A/W at 4.8 V) and detectivity (2 × 1013 Jones at -4.8 V and 4.4 × 1013 Jones at 4.8 V) with ultrafast response of 0.64 μs/47.68 μs (rise/decay). Ultrathin (15 nm) Ga2O3 layer and sophisticated band engineering, combined with suppressed dark current through the interfacial oxygen vacancies on In2O3 layer, enhance the detection performance of the detector at low supply voltage and extremely low light intensity. These results provide a path towards highly sensitive, low-power-consumption and highly-integrated deep-ultraviolet detection, beyond conventional ones.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"87 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797853","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":"One-pot Cascade Conversion of Fructose to 2,5-Diformylfuran Enabled by a Polyionic Liquids based Porous Catalyst","authors":"Gang Liu, Jun Zheng, Xianqiang Huang, Shiqi Fu, Shiqi Xi, Yalin Zhang, Zhen Li, Fei Yu, Yifa Chen","doi":"10.1039/d5qi00135h","DOIUrl":"https://doi.org/10.1039/d5qi00135h","url":null,"abstract":"One-pot direct conversion of cheap and abundant fructose to 2,5-diformylfuran (DFF) is highly sought to achieve hundreds-fold value-increase and high atomic economy yet is still challenging by the lack of suitable catalysts with cascade conversion ability. In this work, we have developed a kind of porous hybrid catalyst (i.e. PMo10V2@2Br-PIL) based on the assembly of polyoxometalates and porous polyionic liquids that can be applied in one-pot conversion of fructose to DFF. The integration of PMo10V2 with 2Br-PIL can impart both Brönsted acid sites and oxidation sites in the porous structure that enables the one-pot cascade conversion. As a result, PMo10V2@2Br-PIL demonstrates remarkable DFF yield (95% yield), satisfying stability, recyclability and scale-up production ability (≈12.3 g in a batch experiment), demonstrating great potential in the industrial production of DFF from fructose. Theoretical calculations reveal the synergistic effect of Brönsted acid sites and oxidation sites in PMo10V2@2Br-PIL that can promote the one-pot conversion of fructose to DFF. This study deepens the insight of biomass transformation over hybrid catalysts by acidic/oxidative synergetic catalysis and contributes to the effort of designing highly active, selective, and multifunctional catalysts for one-pot biomass conversion.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797854","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":"Greatly Enhancing Birefringence of Fluosilicate through the Synergy Effect of Functional Units","authors":"Liang Ma, Yi-Lei Lv, Bing-Wei Miao, Guo-Ren Zhu, Wen-Long Liu, Sheng-Ping Guo, Ru-Ling Tang","doi":"10.1039/d5qi00468c","DOIUrl":"https://doi.org/10.1039/d5qi00468c","url":null,"abstract":"Short-wave ultraviolet optical crystals are widely used in various fields. Exploring organic-inorganic hybrid compounds is an effective approach for discovering crystal materials simultaneously possessing large band gap and birefringence. In this work, two novel organic-inorganic hybrid fluorosilicates, (C2H7N4O)2SiF6 and (C2H4N4)4ZnSiF6·H2O were obtained. (C2H7N4O)2SiF6 has the largest band gap among organic-inorganic hybrid fluorosilicates and unique [(C2H7N4O)2SiF6]∞ layered structure. (C2H4N4)4ZnSiF6·H2O has the largest birefringence (0.282@0.546 μm) among reported organic-inorganic hybrid fluorosilicates. In addition, we systematically analyze the structural and optical properties transformation from (C2H7N4O)2SiF6 to (C2H4N4)4ZnSiF6·H2O.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797850","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 DNA aptamer for trivalent lanthanide ions with low nanomolar affinity","authors":"Jin Wang, Xin Wang, Xuesong Li, Xiangmei Li, Hong-Tao Lei, Juewen Liu","doi":"10.1039/d5qi00391a","DOIUrl":"https://doi.org/10.1039/d5qi00391a","url":null,"abstract":"Lanthanides are extremely important for a variety of technological applications. In this work, DNA aptamers were selected using the library-immobilization method (capture-SELEX) with Tb3+ and Ce3+ as target metal ions. The Tb3+ selection yielded a new sequence named Tb-1 that has a Kd of 26.9 nM for La3+, 3.9 nM for Tb3+, and 2.3 nM for Lu3+ as determined by a DNA strand displacement assay. Binding to other metal ions cannot be detected using a fluorescence DNA strand displacement assay. Therefore, it is a general lanthanide binding aptamer. Another aptamer Tb-4 has some sequence similarity to a previously reported Gd-1 aptamer and it exhibited a Kd of 290 nM, while Gd-1 had a Kd of 1.5 µM, as determined by a thioflavin T fluorescence assay. They showed little selectivity for different lanthanides. Compared to a previously reported aptamer named Sc-1, Tb-1 is an outersphere binder and fast release of bound lanthanides upon the addition of EDTA. By comparing different aptamers, we have gained fundamental insights into aptamer binding to lanthanides. Finally, using the strand displacement reaction, a detection limit of 0.5 nM Tb3+ was achieved in Lake Ontario water.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143789982","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":"Atomically precise Cu14 and Cu13 nanoclusters for oxygen evolution reaction: One additional Cu atom matters","authors":"Ziyi Liu, Pan Zhu, Xianxing Zhou, Lubing Qin, Xunying Liu, Qing Tang, Zhenghua Tang","doi":"10.1039/d5qi00735f","DOIUrl":"https://doi.org/10.1039/d5qi00735f","url":null,"abstract":"Atomically precise coinage metal nanoclusters have been widely explored as model catalysts to study the structure-performance relationship, yet single atom addition onto the metal core to tailor the catalytic properties still remains challenging. Herein, we report a pair of atomically precise Cu nanoclusters, namely [Cu14(Fur)3(PPh3)8H10]+ and [Cu13(Nap)3(PPh3)7H10]0 (hereafter referred to as Cu14 and Cu13, Fur: 2-methyl-3-furanthiolate, Nap: 1-naphthalene thiolate), which exhibit an astonishingly high degree of structural similarity, differing merely by the addition of a single Cu atom yet possessing drastically different catalytic performance toward oxygen evolution reaction (OER). Specifically, in 1 M KOH solution, Cu14 has a much lower overpotential than Cu13 (306 mV vs. 382 mV) to afford a current density of 10 mA cm-2, a smaller Tafel slope and a lower charge transfer resistance. Density functional theory calculations were employed to further identify the catalytic acitve site, confirming that the additonal Cu atom in Cu14 is the key catalytic site which can significantly lower the energy barrier of the rate determining step in OER. This study highlights the crucial role of single-atom addition in modulating the properties and functionalties of atomically precise metal nanoclusters, shedding light on future catalyst design.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"183 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143797855","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}